Thermally stable polymers, method of preparation, and articles made therefrom

ABSTRACT

Multilayer articles are disclosed which comprise: a substrate layer comprising at least one thermoplastic polymer, thermoset polymer, cellulosic material, glass, or metal, and at least one coating layer thereon, said coating layer comprising at least one stabilizer additive and a thermally stable polymer comprising resorcinol arylate polyester chain members substantially free of anhydride linkages linking at least two mers of the polymer chain, prepared by an interfacial method comprising the steps of: (a) combining at least one resorcinol moiety and at least one catalyst in a mixture of water and at least one organic solvent substantially immiscible with water; and (b) adding to the mixture from (a) at least one dicarboxylic acid dichloride while maintaining the pH between 3 and 8.5 through the presence of an acid acceptor, wherein the total molar amount of acid chloride groups is stoichiometrically deficient relative to the total molar amount of phenolic groups.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. application Ser. No.09/368,706, filed Aug. 5, 1999 now U.S. Pat. No. 6,306,507 which claimsthe benefit of U.S. Provisional Application No. 60/134,692, filed May18, 1999, and which applications are incorporated herein by reference.

BACKGROUND OF THE INVENTION

This invention relates to thermally stable polymers comprising polyesterchain members derived from at least one 1,3-dihydroxybenzene moiety andat least one aromatic dicarboxylic acid moiety (often referred tohereinafter as resorcinol arylate chain members), a method for theirpreparation, and multilayer articles made therefrom.

Various polymeric articles have a problem of long term colorinstability. In many cases this instability is seen as yellowing of thepolymer, detracting from its attractiveness and also transparency whenthe polymer was initially transparent. Loss of gloss can also be anundesirable long term phenomenon.

Yellowing of polymers is often caused by the action of ultravioletradiation, and such yellowing is frequently designated “photoyellowing”.Numerous means for suppressing photoyellowing have been employed andproposed. Many of these involve incorporation in the polymer ofultraviolet absorbing compounds (UVA's). For the most part, UVA's arelow molecular weight compounds, which must be employed at relatively lowlevels, typically up to 1% by weight, to avoid degradation of thephysical properties of the polymer such as impact strength and hightemperature properties as reflected in heat distortion temperature.Another problem of concern with polymers such as aromatic polycarbonatesand addition polymers of alkenylaromatic compounds such as styrene issusceptibility to attack by organic liquids.

One way of protecting a resinous article against photoyellowing and lossof gloss is to apply a coating of a weatherable second polymer, the term“weatherable” as used herein signifying resistance to such phenomena.Coatings made from polyesters containing resorcinol arylate units oftenpossess good weatherability properties. The arylate moieties typicallycontain isophthalate, terephthalate, and especially mixtures of iso- andterephthalate units. Polyesters of resorcinol with mixtures ofisophthalate and terephthalate chain members typically have goodweatherability properties and may provide protection againstphotoyellowing when coated over a resinous substrate.

The good weatherability properties of polyesters containing resorcinolarylate units are believed to arise in large part from the screeningeffect said polymers may provide to ultraviolet (UV) light. On exposureto UV light polymers comprising resorcinol arylate chain members mayundergo photochemical Fries rearrangement converting at least a portionof the polymer from polyester chain members too-hydroxybenzophenone-type chain members. The o-hydroxybenzophenone-typechain members act to screen further UV light and protect UV-sensitivecomponents in a resorcinol arylate-containing composition. The goodweatherability properties of polymers comprising resorcinol arylatechain members make them especially useful in blends and in multilayerarticles in which said polymers may act as a protecting layer for moresensitive substrate components.

Copolyesters comprising resorcinol iso- and terephthalate polyesterchain members in combination with diacid or diol alkylene chain members(so-called “soft-block” chain members) are disclosed in commonly ownedU.S. Pat. No. 5,916,997. These copolymers have excellent weatherabilityand flexibility. Copolyestercarbonates comprising resorcinol iso- andterephthalate polyester chain members in combination with carbonatechain members are disclosed in commonly owned, co-pending applicationSer. No. 09/416,529, filed Oct. 12, 1999. These copolymers haveexcellent weatherability and are compatible with polycarbonates inblends.

Polyesters containing resorcinol arylate chain members have beenprepared by melt methods as disclosed in U.S. Pat. No. 4,127,560 and inJapanese Kokai 1/201,326. The methods may provide polyesters containingisophthalate and terephthalate chain members but do not allow theincorporation of greater than 30 mole % terephthalate. In addition, thepolyesters obtained have unacceptable color.

Polyesters containing resorcinol arylate chain members have also beenprepared by an interfacial method. The interfacial method comprises asolvent mixture containing water and at least one organic solventsubstantially immiscible with water. According to U.S. Pat. No.3,460,961 and Eareckson, Journal of Polymer Science, vol. XL, pp.399-406 (1959), preparation of resorcinol arylate polyesters with amixture of iso- and terephthalate chain members is performed by aninterfacial method in water and a water-immiscible solvent such aschloroform or dichloromethane using 1:1 stoichiometric ratio ofresorcinol to either iso- or terephthaloyl dichloride, or a mixturethereof, in the presence of aqueous sodium hydroxide. The resorcinol iscombined with the aqueous sodium hydroxide before addition of acidchlorides, and the reaction is run at pH which is initially high butwhich decreases as the reaction proceeds. The molecular weight of thepolymers is not controlled. The method provides polymer with very highweight average molecular weight (Mw), making the polymer unsuitable forsome applications. Furthermore, the polymer has poor thermal stabilityand loses molecular weight upon thermal treatment.

Multilayer articles containing layers made from resorcinolarylate-containing polyester have been described by Cohen et al.,Journal of Polymer Science: Part A-1, vol. 9, 3263-3299 (1971) and inU.S. Pat. No. 3,460,961. The polyester was made either in solution or byan interfacial process. The solution method requires the use of astoichiometric amount of an organic base, such as a tertiary amine,which must be isolated and recovered for reuse in any economical,environmentally friendly process. Both methods produce thermallyunstable polyester which can only be applied by solution coatingfollowed by evaporation of the solvent to make a multilayer article.This solution coating method has numerous deficiencies, some of whichare mentioned in the Cohen et al. paper at page 3267: namely, thenecessity to use high priced and toxic solvents, the inherently lowconcentration of the arylate polymer in the solvent and the tendency ofthe solutions to gel. Accordingly, the described polyesters wereconsidered “unacceptable coating candidates”.

Japanese Kokai 1/199,841 discloses articles having a substrate layercomprising at least 90 mole percent poly(ethylene terephthalate) and agas barrier coating layer which is a polyester of resorcinol and aminimum of 50 mole % isophthalic acid, optionally with copolyester unitsderived from another dicarboxylic acid such as terephthalic acid,naphthalenedicarboxylic acid or various other specifically nameddicarboxylic acids. The disclosed articles may be prepared by a seriesof operations including co-injection molding. However, the only types ofarticles disclosed are bottles, which are produced from a co-injectionmolded parison by subsequent blow molding. Larger articles, such asexternal automobile body parts, are not disclosed and no method fortheir production is suggested, nor are articles in which the substratelayer is anything other than poly(ethylene terephthalate). In addition,the resorcinol isophthalate polyesters were prepared either by meltmethods which do not allow the incorporation of greater than 30 mole %terephthalate and give polyester with unacceptable color, or by theinterfacial method which produces thermally unstable polyester.

It remains of interest, therefore, to develop a method for preparingweatherable, solvent resistant multilayer articles which are capable ofuse for such varied purposes as body parts for outdoor vehicles anddevices such as automobiles. There is also a particular need forpolymers comprising resorcinol arylate chain members having controlledmolecular weight, high thermal stability, and low color. There is also aparticular need for polymers comprising resorcinol arylate chain membersthat can be processed using typical melt processing techniques.

BRIEF SUMMARY OF THE INVENTION

The present inventors have identified the primary source of poor thermalstability in polymers comprising resorcinol arylate polyester chainmembers prepared by the interfacial method, and have discovered a methodto prepare said polymers in thermally stable form with controlledmolecular weight. The new method also allows the preparation ofvirtually colorless polymers comprising resorcinol arylate polyesterchain members.

In one of its aspects the present invention provides an interfacialmethod for preparing polymers comprising resorcinol arylate polyesterchain members substantially free of anhydride linkages linking at leasttwo mers of the polymer chain, comprising the steps of:

(a) combining at least one resorcinol moiety and at least one catalystin a mixture of water and at least one organic solvent substantiallyimmiscible with water; and

(b) adding to the mixture from (a) at least one dicarboxylic aciddichloride while maintaining the pH between 3 and 8.5 through thepresence of an acid acceptor, wherein the total molar amount of acidchloride groups is stoichiometrically deficient relative to the totalmolar amount of phenolic groups.

In another of its aspects the invention provides a polymer consistingessentially of resorcinol arylate polyester chain members substantiallyfree of anhydride linkages linking at least two mers of the polymerchain, prepared by an interfacial method comprising the above steps.

In yet another of its aspects the invention provides a copolymerconsisting essentially of resorcinol arylate polyester chain members incombination with C₃₋₂₀ straight chain alkylene, C₃₋₁₀ branched alkylene,or C₄₋₁₀ cyclo- or bicycloalkylene chain members, substantially free ofanhydride linkages linking at least two mers of the polymer chain,prepared by an interfacial method comprising the above steps.

In still another of its aspects the invention provides a copolymerconsisting essentially of resorcinol arylate polyester chain members incombination with organic carbonate chain members, substantially free ofanhydride linkages linking at least two mers of the polymer chain,prepared by an interfacial method, comprising the above steps.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment the present invention comprises an interfacial methodfor preparing thermally stable polymers comprising resorcinol arylatepolyester chain members which derive their thermal stability in largepart from being substantially free of anhydride linkages in the polymerchains. In another embodiment the present invention comprises thethermally stable polymers prepared by such an interfacial method.

Thermal stability within the context of the present invention refers toresistance of a polymer to molecular weight degradation under thermalconditions. Thus, a polymer with poor thermal stability showssignificant molecular weight degradation under thermal conditions, suchas during extrusion, molding, thermoforming, hot-pressing, and likeconditions. Molecular weight degradation may also be manifest throughcolor formation and/or in the degradation of other properties such asweatherability, gloss, mechanical properties, and/or thermal properties.Molecular weight degradation can also cause significant variation inprocessing conditions as the melt viscosity changes.

In one of its aspects the method of the present invention providesthermally stable polymers comprising arylate polyester chain members.Said chain members comprise at least one diphenol residue in combinationwith at least one aromatic dicarboxylic acid residue. In one embodimentthe diphenol residue is derived from a 1,3-dihydroxybenzene moiety, asillustrated in Formula I, commonly referred to throughout thisspecification as resorcinol or resorcinol moiety. Resorcinol orresorcinol moiety as used within the context of the present inventionshould be understood to include both unsubstituted 1,3-dihydroxybenzeneand substituted 1,3-dihydroxybenzenes unless explicitly statedotherwise.

In Formula I R is at least one of C₁₋₁₂ alkyl or halogen, and n is 0-3.

Suitable dicarboxylic acid residues include aromatic dicarboxylic acidresidues derived from monocyclic moieties. In various embodimentssuitable dicarboxylic acid residues include those derived fromisophthalic acid, terephthalic acid, or mixtures of isophthalic andterephthalic acids. Suitable dicarboxylic acid residues also includethose derived from polycyclic moieties, illustrative examples of whichinclude diphenyl dicarboxylic acid, diphenylether dicarboxylic acid, andnaphthalenedicarboxylic acid, especially naphthalene-2,6-dicarboxylicacid. In some embodiments the aromatic dicarboxylic acid residues arederived from mixtures of isophthalic and/or terephthalic acids astypically illustrated in Formula II.

Therefore, in one embodiment the present invention provides thermallystable polymers comprising resorcinol arylate polyester chain members astypically illustrated in Formula III wherein R and n are as previouslydefined:

Previous interfacial methods for preparing polyesters comprisingresorcinol arylate chain members typically provide polymers with poorthermal stability and uncontrolled molecular weight. The presentinventors have discovered that a primary reason for poor thermalstability is the presence of anhydride linkages in the backbone of thepolyester chain. Typical anhydride linkages are illustrated in FormulaIV. Such anhydride linkages link at least two mers in a polymer chainand may arise through combination of two isophthalate or terephthalatemoieties or mixtures thereof, although it is to be understood thatanhydride linkages in polymers comprising resorcinol arylate chainmembers may arise through combination of any suitable similardicarboxylic acid residues or mixtures of suitable dissimilardicarboxylic acid residues present in a reaction mixture.

Although the invention is not limited by theory, it is believed that theanhydride linkage represents a weak bond in the polyester chain, whichcan break under thermal processing conditions to produce shorter chainsterminated by acid end-groups. These acid end-groups, in turn, mayaccelerate the hydrolysis of the arylate moiety, generating additionalcarboxyl and hydroxyl end-groups, and further contributing to themolecular weight degradation, and loss in other desirable properties.Anhydride linkages may arise through several mechanisms. In onemechanism a carboxylic acid chloride may be hydrolyzed to carboxylicacid when the esterification reaction is run at high pH. The carboxylicacid or corresponding carboxylate may then react with another carboxylicacid chloride to yield an anhydride linkage.

Anhydride linkages may be detected by means known to those skilled inthe art such as by ¹³C nuclear magnetic resonance spectroscopy (NMR).For example, resorcinol arylate polyesters comprising dicarboxylic acidresidues derived from a mixture of iso- and terephthalic acids typicallyshow ¹³C NMR resonances attributed to anhydride at 161.0 and 161.1 ppm(in deuterochloroform relative to tetramethylsilane), as well asresonances for the polymer carboxylic acid and hydroxyl end-groups.After thermal processing (for example, extrusion and/or molding), thepolymer molecular weight decreases, and the anhydride resonancestypically decrease, while those of the acid and hydroxyl end-groupstypically increase.

Anhydride linkages in polymers comprising resorcinol arylate polyesterchain members may also be detected by reaction of polymer with anucleophile, such as a secondary amine. For example, resorcinol arylatepolyesters comprising dicarboxylic acid residues derived from a mixtureof iso- and terephthalic acids can be dissolved in a convenient solvent,such as dichloromethane, and treated with a secondary amine, such asdibutylamine or diisobutylamine, for several minutes at ambienttemperature. Comparison of the starting polymer molecular weight to thatafter amine treatment typically shows a decrease in molecular weightwhich can be correlated with the corresponding decrease observed undertypical thermal processing conditions. Although the invention is notmeant to be limited by theory, it is believed that nucleophiles, such assecondary amine and phenolic, attack anhydride linkages (as opposed toester linkages) selectively under the reaction conditions. The decreasein molecular weight upon reaction with amine nucleophile is therefore anindication of the presence of anhydride functionality in the polymer.

In one of its aspects the present invention provides an interfacialmethod for preparing polymers comprising resorcinol arylate polyesterchain members substantially free of anhydride linkages, said methodcomprising a first step of combining at least one resorcinol moiety andat least one catalyst in a mixture of water and at least one organicsolvent substantially immiscible with water. Suitable resorcinolmoieties comprise units of Formula V:

wherein R is at least one of C₁₋₁₂ alkyl or halogen, and n is 0-3. Alkylgroups, if present, are typically straight-chain, branched, or cyclicalkyl groups, and are most often located in the ortho position to bothoxygen atoms although other ring locations are contemplated. SuitableC₁₋₁₂ alkyl groups include, but are not limited to, methyl, ethyl,n-propyl, isopropyl, butyl, iso-butyl, t-butyl, hexyl, cyclohexyl,nonyl, decyl, and aryl-substituted alkyl, including benzyl. In aparticular embodiment an alkyl group is methyl. Suitable halogen groupsare bromo, chloro, and fluoro. The value for n in various embodimentsmay be 0-3, in some embodiments 0-2, and in still other embodiments 0-1.In one embodiment a resorcinol moiety is 2-methylresorcinol. In anotherembodiment the resorcinol moiety is an unsubstituted resorcinol moietyin which n is zero.

The method further comprises combining at least one catalyst with thereaction mixture. Said catalyst may be present in various embodiments ata total level of 0.1 to 10 mole %, and in some embodiments at a totallevel of 0.2 to 6 mole % based on total molar amount of acid chloridegroups. Suitable catalysts comprise tertiary amines, quaternary ammoniumsalts, quaternary phosphonium salts, hexaalkylguanidinium salts, andmixtures thereof. Suitable tertiary amines include triethylamine,dimethylbutylamine, diisopropylethylamine,2,2,6,6-tetramethylpiperidine, and mixtures thereof. Other contemplatedtertiary amines include N-C₁-C₆-alkyl-pyrrolidines, such asN-ethylpyrrolidine, N-C₁-C₆-piperidines, such as N-ethylpiperidine,N-methylpiperidine, and N-isopropylpiperidine, N-C₁-C₆-morpholines, suchas N-ethylmorpholine and N-isopropyl-morpholine, N-C₁-C₆-dihydroindoles,N-C₁-C₆-dihydroisoindoles, N-C₁-C₆-tetrahydroquinolines,N-C₁-C₆-tetrahydroisoquinolines, N-C₁-C₆-benzo-morpholines,1-azabicyclo-[3.3.0]-octane, quinuclidine,N-C₁-C₆-alkyl-2-azabicyclo-[2.2.1]-octanes,N-C₁-C₆-alkyl-2-azabicyclo-[3.3.1]-nonanes, andN-C₁-C₆-alkyl-3-azabicyclo-[3.3.1]-nonanes,N,N,N′,N′-tetraalkylalkylene-diamines, includingN,N,N′,N′-tetraethyl-1,6-hexanediamine. In various embodiments tertiaryamines are triethylamine and N-ethylpiperidine.

When the catalyst consists of at least one tertiary amine alone, thensaid catalyst may be present in one embodiment at a total level of 0.1to 10 mole %, in another embodiment at a total level of 0.2 to 6 mole %,in another embodiment at a total level of 1 to 4 mole %, and in stillanother embodiment at a total level of 2.5 to 4 mole % based on totalmolar amount of acid chloride groups. In one embodiment of the inventionall of the at least one tertiary amine is present at the beginning ofthe reaction before addition of dicarboxylic acid dichloride toresorcinol moiety. In another embodiment a portion of any tertiary amineis present at the beginning of the reaction and a portion is addedfollowing or during addition of dicarboxylic acid dichloride toresorcinol moiety. In this latter embodiment the amount of any tertiaryamine initially present with resorcinol moiety may range in oneembodiment from about 0.005 wt. % to about 10 wt. %, in anotherembodiment from about 0.01 to about 1 wt. %, and in still anotherembodiment from about 0.02 to about 0.3 wt. % based on total amine.

Suitable quaternary ammonium salts, quaternary phosphonium salts, andhexaalkylguanidinium salts include halide salts such astetraethylammonium bromide, tetraethylammonium chloride,tetrapropylammonium bromide, tetrapropylammonium chloride,tetrabutylammonium bromide, tetrabutylammonium chloride,methyltributylammonium chloride, benzyltributylammonium chloride,benzyltriethylammonium chloride, benzyltrimethylammonium chloride,trioctylmethylammonium chloride, cetyldimethylbenzylammonium chloride,octyltriethylammonium bromide, decyltriethylammonium bromide,lauryltriethylammonium bromide, cetyltrimethylammonium bromide,cetyltriethylammonium bromide, N-laurylpyridinium chloride,N-laurylpyridinium bromide, N-heptylpyridinium bromide,tricaprylylmethylammonium chloride (sometimes known as ALIQUAT 336),methyltri-C₈-C₁₀-alkyl-ammonium chloride (sometimes known as ADOGEN464), N,N,N′,N′,N′-pentaalkyl-alpha, omega-amine-ammonium salts such asdisclosed in U.S. Pat. No. 5,821,322; tetrabutylphosphonium bromide,benzyltriphenylphosphonium chloride, triethyloctadecylphosphoniumbromide, tetraphenylphosphonium bromide, triphenylmethylphosphoniumbromide, trioctylethylphosphonium bromide, cetyltriethylphosphoniumbromide, hexaalkylguanidinium halides, hexaethylguanidinium chloride,and the like, and mixtures thereof.

Organic solvents substantially immiscible with water include those whichin one embodiment are less than about 5 wt. %, and in another embodimentless than about 2 wt. % soluble in water under the reaction conditions.Suitable organic solvents include dichloromethane, trichloroethylene,tetrachloroethane, chloroform, 1,2-dichloroethane, toluene, xylene,trimethylbenzene, chlorobenzene, o-dichlorobenzene, and mixturesthereof. In a particular embodiment the solvent is dichloromethane.

Suitable dicarboxylic acid dichlorides may comprise aromaticdicarboxylic acid dichlorides derived from monocyclic moieties,illustrative examples of which include isophthaloyl dichloride,terephthaloyl dichloride, or mixtures of isophthaloyl and terephthaloyldichlorides. Suitable dicarboxylic acid dichlorides may also comprisearomatic dicarboxylic acid dichlorides derived from polycyclic moieties,illustrative examples of which include diphenyl dicarboxylic aciddichloride, diphenylether dicarboxylic acid dichloride, andnaphthalenedicarboxylic acid dichloride, especiallynaphthalene-2,6-dicarboxylic acid dichloride; or from mixtures ofmonocyclic and polycyclic aromatic dicarboxylic acid dichlorides. In oneembodiment the dicarboxylic acid dichloride comprises mixtures ofisophthaloyl and/or terephthaloyl dichlorides as typically illustratedin Formula VI.

Either or both of isophthaloyl and terephthaloyl dichlorides may bepresent. In some embodiments the dicarboxylic acid dichlorides comprisemixtures of isophthaloyl and terephthaloyl dichloride in a molar ratioof isophthaloyl to terephthaloyl of about 0.25-4.0:1; in otherembodiments the molar ratio is about 0.4-2.5:1; and in still otherembodiments the molar ratio is about 0.67-1.5:1.

The pH of the reaction mixture is maintained in some embodiments betweenabout 3 and about 8.5, and in other embodiments between about 5 andabout 8, throughout addition of the at least one dicarboxylic aciddichloride to the at least one resorcinol moiety. Suitable reagents tomaintain the pH include alkali metal hydroxides, alkaline earthhydroxides, and alkaline earth oxides. In some embodiments the reagentsare potassium hydroxide and sodium hydroxide. In a particular embodimentthe reagent is sodium hydroxide. The reagent to maintain pH may beincluded in the reaction mixture in any convenient form. In someembodiments said reagent is added to the reaction mixture as an aqueoussolution simultaneously with the at least one dicarboxylic aciddichloride.

The temperature of the reaction mixture may be any convenienttemperature that provides a rapid reaction rate and a resorcinolarylate-containing polymer substantially free of anhydride linkages.Convenient temperatures include those from about −20° C. to the boilingpoint of the water-organic solvent mixture under the reactionconditions. In one embodiment the reaction is performed at the boilingpoint of the organic solvent in the water-organic solvent mixture. Inanother embodiment the reaction is performed at the boiling point ofdichloromethane.

The total molar amount of acid chloride groups added to the reactionmixture is stoichiometrically deficient relative to the total molaramount of phenolic groups. Said stoichiometric ratio is desirable sothat hydrolysis of acid chloride groups is minimized, and so thatnucleophiles such as phenolic and/or phenoxide may be present to destroyany adventitious anhydride linkages, should any form under the reactionconditions. The total molar amount of acid chloride groups includes theat least one dicarboxylic acid dichloride, and any mono-carboxylic acidchloride chain-stoppers and any tri- or tetra-carboxylic acid tri- ortetra-chloride branching agents which may be used. The total molaramount of phenolic groups includes resorcinol moieties, and anymono-phenolic chain-stoppers and any tri- or tetra-phenolic branchingagents which may be used. The stoichiometric ratio of total phenolicgroups to total acid chloride groups is in one embodiment about1.5-1.01:1 and in another embodiment about 1.2-1.02:1.

The presence or absence of adventitious anhydride linkages followingcomplete addition of the at least one dicarboxylic acid dichloride tothe at least one resorcinol moiety will typically depend upon the exactstoichiometric ratio of reactants and the amount of catalyst present, aswell as other variables. For example, if a sufficient molar excess oftotal phenolic groups is present, anhydride linkages are often found tobe absent. In one embodiment a molar excess of at least about 1% and inanother embodiment a molar excess of at least about 3% of total amountof phenolic groups over total amount of acid chloride groups may sufficeto eliminate anhydride linkages under the reaction conditions. Whenanhydride linkages may be present, it is often desirable that the finalpH be greater than 7 so that nucleophiles such as phenolic, phenoxideand/or hydroxide may be present to destroy any adventitious anhydridelinkages. Therefore, in various embodiments the method of the inventionmay further comprise the step of adjusting the pH of the reactionmixture in one embodiment to between 7 and 12, in another embodiment tobetween 8 and 12, and in still another embodiment to between 8.5 and 12,following complete addition of the at least one dicarboxylic aciddichloride to the at least one resorcinol moiety. The pH may be adjustedby any convenient method; in one embodiment the pH is adjusted using anaqueous base such as aqueous sodium hydroxide.

Provided the final pH of the reaction mixture is greater than 7, themethod of the invention in another embodiment may further comprise thestep of stirring the reaction mixture for a time sufficient to destroycompletely any adventitious anhydride linkages, should any be present.The necessary stirring time will depend upon reactor configuration,stirrer geometry, stirring rate, temperature, total solvent volume,organic solvent volume, anhydride concentration, pH, and other factors.In some instances the necessary stirring time is essentiallyinstantaneous, for example within seconds of pH adjustment to above 7,assuming any adventitious anhydride linkages were present to begin with.For typical laboratory scale reaction equipment a stirring time may berequired in one embodiment of at least about 3 minutes, and in anotherembodiment of at least about 5 minutes. By this process nucleophiles,such as phenolic, phenoxide and/or hydroxide, may have time to destroycompletely any adventitious anhydride linkages, should any be present.

At least one chain-stopper (also referred to sometimes hereinafter ascapping agent) may also be present in the method and compositions of theinvention. A purpose of adding at least one chain-stopper is to limitthe molecular weight of polymer comprising resorcinol arylate polyesterchain members, thus providing polymer with controlled molecular weightand favorable processability. Typically, at least one chain-stopper isadded when the resorcinol arylate-containing polymer is not required tohave reactive end-groups for further application. In the absence ofchain-stopper resorcinol arylate-containing polymer may be either usedin solution or recovered from solution for subsequent use such as incopolymer formation which may require the presence of reactiveend-groups, typically hydroxy, on the resorcinolarylate polyestersegments. A chain-stopper may be at least one of mono-phenoliccompounds, mono-carboxylic acid chlorides, and/or mono-chloroformates.Typically, the at least one chain-stopper may be present in quantitiesof 0.05 to 10 mole %, based on resorcinol moieties in the case ofmono-phenolic compounds and based on acid dichlorides in the casemono-carboxylic acid chlorides and/or mono-chloroformates.

Suitable mono-phenolic compounds include monocyclic phenols, such asphenol, C₁-C₂₂ alkyl-substituted phenols, p-cumyl-phenol,p-tertiary-butyl phenol, hydroxy diphenyl; monoethers of diphenols, suchas p-methoxyphenol. Alkyl-substituted phenols include those withbranched chain alkyl substituents having 8 to 9 carbon atoms, preferablyin which about 47 to 89% of the hydrogen atoms are part of methyl groupsas described in U.S. Pat. No. 4,334,053. For some embodiments amono-phenolic UV absorber is used as capping agent. Such compoundsinclude 4-substituted-2-hydroxybenzophenones and their derivatives, arylsalicylates, monoesters of diphenols, such as resorcinol monobenzoate,2-(2-hydroxyaryl)benzotriazoles and their derivatives,2-(2-hydroxyaryl)-1,3,5-triazines and their derivatives, and likecompounds. In some embodiments mono-phenolic chain-stoppers are phenol,p-cumylphenol, and resorcinol monobenzoate.

Suitable mono-carboxylic acid chlorides include monocyclic,mono-carboxylic acid chlorides, such as benzoyl chloride, C₁-C₂₂alkyl-substituted benzoyl chloride, toluoyl chloride,halogen-substituted benzoyl chloride, bromobenzoyl chloride, cinnamoylchloride, 4-nadimidobenzoyl chloride, and mixtures thereof; polycyclic,mono-carboxylic acid chlorides, such as trimellitic anhydride chloride,and naphthoyl chloride; and mixtures of monocyclic and polycyclicmono-carboxylic acid chlorides. The chlorides of aliphaticmonocarboxylic acids with up to 22 carbon atoms are also suitable.Functionalized chlorides of aliphatic monocarboxylic acids, such asacryloyl chloride and methacryoyl chloride, are also suitable. Suitablemono-chloroformates include monocyclic, mono-chloroformates, such asphenyl chloroformate, alkyl-substituted phenyl chloroformate, p-cumylphenyl chloroformate, toluene chloroformate, and mixtures thereof.

A chain-stopper can be combined together with the resorcinol moieties,can be contained in the solution of dicarboxylic acid dichlorides, orcan be added to the reaction mixture after production of aprecondensate. If mono-carboxylic acid chlorides and/ormono-chloroformates are used as chain-stoppers, they are oftenintroduced together with dicarboxylic acid dichlorides. Thesechain-stoppers can also be added to the reaction mixture at a momentwhen the chlorides of dicarboxylic acid have already reactedsubstantially or to completion. If phenolic compounds are used aschain-stoppers, they can be added in one embodiment to the reactionmixture during the reaction, or, in another embodiment, before thebeginning of the reaction between resorcinol moiety and acid chloridemoiety. When hydroxy-terminated resorcinol arylate-containingprecondensate or oligomers are prepared, then chain-stopper may beabsent or only present in small amounts to aid control of oligomermolecular weight.

In another embodiment the invention may encompass the inclusion of atleast one branching agent such as a trifunctional or higher functionalcarboxylic acid chloride and/or trifunctional or higher functionalphenol. Such branching agents, if included, can typically be used inquantities of 0.005 to 1 mole %, based on dicarboxylic acid dichloridesor resorcinol moieties used, respectively. Suitable branching agentsinclude, for example, trifunctional or higher carboxylic acid chlorides,such as trimesic acid trichloride, cyanuric acid trichloride,3,3′,4,4′-benzophenone tetracarboxylic acid tetrachloride,1,4,5,8-naphthalene tetracarboxylic acid tetrachloride or pyromelliticacid tetrachloride, and trifunctional or higher phenols, such asphloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-2-heptene,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane,1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane,tri-(4-hydroxyphenyl)-phenyl methane,2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane,2,4-bis-(4-hydroxyphenylisopropyl)-phenol,tetra-(4-hydroxyphenyl)-methane,2,6-bis-(2-hydroxy-5-methylbenzyl)-4-methyl phenol,2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane,tetra-(4-[4-hydroxyphenylisopropyl]-phenoxy)-methane,1,4-bis-[(4,4-dihydroxytriphenyl)methyl]-benzene. Phenolic branchingagents may be introduced first with the resorcinol moieties whilst acidchloride branching agents may be introduced together with aciddichlorides.

For some applications such as for copolymer formation the resorcinolarylate-containing polymer may remain in solution for subsequent processsteps. In other instances such as in the production of resorcinolarylate polyester the polymer will normally be isolated from solution.Therefore, in another embodiment of the invention the resorcinolarylate-containing polymer is recovered from the reaction mixture.Recovery methods are well known to those skilled in the art and mayinclude such steps as acidification of the mixture, for example withphosphorous acid; subjecting the mixture to liquid-liquid phaseseparation; washing the organic phase with water and/or a dilute acidsuch as hydrochloric acid or phosphoric acid; precipitating by usualmethods such as through treatment with water or anti-solventprecipitation with, for example, methanol, ethanol, and/or isopropanol;isolating the resulting precipitates; and drying to remove residualsolvents.

If desired, the resorcinol arylate polymers of the invention may be madeby the present method further comprising the addition of a reducingagent. Suitable reducing agents include, for example, sodium sulfite,sodium gluconate, or a borohydride, such as sodium borohydride. Whenpresent, any reducing agents are typically used in quantities of from0.25 to 2 mole %, based on moles of resorcinol moiety.

In one of its embodiments the invention comprises thermally stableresorcinol arylate polyesters made by the present method andsubstantially free of anhydride linkages linking at least two mers ofthe polyester chain. In a particular embodiment said polyesters comprisedicarboxylic acid residues derived from a mixture of iso- andterephthalic acids as illustrated in Formula VII:

wherein R is at least one of C₁₋₁₂ alkyl or halogen, n is 0-3, and m isat least about 8. In various embodiments n is zero and m is betweenabout 10 and about 300. The molar ratio of isophthalate to terephthalateis in one embodiment about 0.25-4.0:1, in another embodiment about0.4-2.5:1, and in still another embodiment about 0.67-1.5:1.Substantially free of anhydride linkages means that said polyesters showdecrease in molecular weight in one embodiment of less than 30% and inanother embodiment of less than 10% upon heating said polymer at atemperature of about 280-290° C. for five minutes.

The present invention also encompasses thermally stable copolymerscontaining segments comprising resorcinol arylate polyester chainmembers made by the present method and substantially free of anhydridelinkages linking at least two mers of the copolymer chain. Thus, inanother of its embodiments the present invention comprises thermallystable copolyesters comprising resorcinol arylate polyester chainmembers in combination with dicarboxylic acid or diol alkylene chainmembers (so-called “soft-block” segments), said copolyesters beingsubstantially free of anhydride linkages in the polyester segments.Substantially free of anhydride linkages means that the copolyestersshow decrease in molecular weight in one embodiment of less than 10% andin another embodiment of less than 5% upon heating said copolyester at atemperature of about 280-290° C. for five minutes. Related copolyesterscontaining soft-block segments are disclosed in commonly owned U.S. Pat.No. 5,916,997.

The term soft-block as used herein, indicates that some segments of thepolymers are made from non-aromatic monomer units. Such non-aromaticmonomer units are generally aliphatic and are known to impartflexibility to the soft-block-containing polymers. The copolymersinclude those comprising structural units of Formulas I, VIII, and IX:

wherein R and n are as previously defined, Z is a divalent aromaticradical, R² is a C₃₋₂₀ straight chain alkylene, C₃₋₁₀ branched alkylene,or C₄₋₁₀ cyclo- or bicycloalkylene group, and R³ and R⁴ eachindependently represent

wherein Formula IX contributes from about 1 to about 45 mole percent tothe ester linkages of the polyester. Additional embodiments of thepresent invention provide a composition wherein Formula IX contributesin various embodiments from about 5 to about 40 mole percent to theester linkages of the polyester, and in other embodiments from about 5to about 20 mole percent to the ester linkages of the polyester. Anotherembodiment provides a composition wherein R² represents in oneembodiment C₃₋₁₄ straight chain alkylene, or C₅₋₆ cycloalkylene, and inanother embodiment R² represents C₃₋₁₀ straight-chain alkylene orC₆-cycloalkylene. Formula VIII represents an aromatic dicarboxylic acidresidue. The divalent aromatic radical Z in Formula VIII may be derivedin various embodiments from at least one of the suitable dicarboxylicacid residues as defined hereinabove, and in some embodiments at leastone of 1,3-phenylene, 1,4-phenylene, or 2,6-naphthylene. In variousembodiments Z comprises at least about 40 mole percent 1,3-phenylene. Invarious embodiments of copolyesters containing soft-block chain membersn in Formula I is zero.

In various embodiments copolyesters containing resorcinol arylate chainmembers are those comprising from about 1 to about 45 mole % sebacate orcyclohexane-1,4-dicarboxylate units. In a particular embodiment acopolyester containing resorcinol arylate chain members is onecomprising resorcinol isophthalate and resorcinol sebacate units inmolar ratio between 8.5:1.5 and 9.5:0.5. In one embodiment saidcopolyester is prepared using sebacoyl chloride in combination withisophthaloyl dichloride.

In another of its embodiments the present invention comprises thermallystable block copolyestercarbonates comprising resorcinolarylate-containing block segments in combination with organic carbonateblock segments. The segments comprising resorcinol arylate chain membersin such copolymers are substantially free of anhydride linkages.Substantially free of anhydride linkages means that thecopolyestercarbonates show decrease in molecular weight in oneembodiment of less than 10% and in another embodiment of less than 5%upon heating said copolyestercarbonate at a temperature of about280-290° C. for five minutes. Related block copolyestercarbonates aredisclosed in commonly owned, co-pending application Ser. No. 09/416,529,filed Oct. 12, 1999.

The block copolyestercarbonates include those comprising alternatingarylate and organic carbonate blocks, typically as illustrated inFormula X, wherein R and n are as previously defined, and R⁵ is at leastone divalent organic radical:

The arylate blocks have a degree of polymerization (DP), represented bym, in one embodiment of at least about 4, in another embodiment of atleast about 10, in another embodiment of at least about 20 and in stillanother embodiment of about 30-150. The DP of the organic carbonateblocks, represented by p, is in one embodiment generally at least about10, in another embodiment at least about 20 and in still anotherembodiment about 50-200. The distribution of the blocks may be such asto provide a copolymer having any desired weight proportion of arylateblocks in relation to carbonate blocks. In general, the content ofarylate blocks is in one embodiment about 10-95% by weight and inanother embodiment about 50-95% by weight.

Although a mixture of iso- and terephthalate is illustrated in FormulaX, the dicarboxylic acid residues in the arylate blocks may be derivedfrom any suitable dicarboxylic acid residue, as defined hereinabove, ormixture of suitable dicarboxylic acid residues, including those derivedfrom aliphatic diacid dichlorides (so-called “soft-block” segments). Invarious embodiments n is zero and the arylate blocks comprisedicarboxylic acid residues derived from a mixture of iso- andterephthalic acid residues, wherein the molar ratio of isophthalate toterephthalate is in one embodiment about 0.25-4.0:1, in anotherembodiment about 0.4-2.5:1, and in still another embodiment about0.67-1.5:1.

In the organic carbonate blocks, each R⁵ is independently a divalentorganic radical. In various embodiments said radical comprises at leastone dihydroxy-substituted aromatic hydrocarbon, and at least about 60percent of the total number of R⁵ groups in the polymer are aromaticorganic radicals and the balance thereof are aliphatic, alicyclic, oraromatic radicals. Suitable R⁵ radicals include m-phenylene,p-phenylene, 4,4′-biphenylene, 4,4′-bi(3,5-dimethyl)-phenylene,2,2-bis(4-phenylene)propane,6,6′-(3,3,3′,3′-tetramethyl-1,1-spirobi[1H-indan]) and similar radicalssuch as those which correspond to the dihydroxy-substituted aromatichydrocarbons disclosed by name or formula (generic or specific) in U.S.Pat. No. 4,217,438.

In some embodiments each R⁵ is an aromatic organic radical and in otherembodiments a radical of Formula XI:

wherein each A¹ and A² is a monocyclic divalent aryl radical and Y is abridging radical in which one or two carbon atoms separate A¹ and A².The free valence bonds in Formula XI are usually in the meta or parapositions of A¹ and A² in relation to Y. Compounds in which R⁵ hasFormula XI are bisphenols, and for the sake of brevity the term“bisphenol” is sometimes used herein to designate thedihydroxy-substituted aromatic hydrocarbons. It should be understood,however, that non-bisphenol compounds of this type may also be employedas appropriate.

In Formula XI, A¹ and A² typically represent unsubstituted phenylene orsubstituted derivatives thereof, illustrative substituents (one or more)being alkyl, alkenyl, and halogen (particularly bromine). In oneembodiment unsubstituted phenylene radicals are preferred. Both A¹ andA² are often p-phenylene, although both may be o- or m-phenylene or oneo- or m-phenylene and the other p-phenylene.

The bridging radical, Y, is one in which one or two atoms, separate A¹from A². In a particular embodiment one atom separates A¹ and A².Illustrative radicals of this type are —O—, —S—, —SO— or —SO₂—,methylene, cyclohexyl methylene, 2-[2.2.1]-bicycloheptyl methylene,ethylene, isopropylidene, neopentylidene, cyclohexylidene,cyclopentadecylidene, cyclododecylidene, adamantylidene, and likeradicals.

In some embodiments gem-alkylene (commonly known as “alkylidene”)radicals are preferred. Also included, however, are unsaturatedradicals. In some embodiments the preferred bisphenol is2,2-bis(4-hydroxyphenyl)propane (bisphenol-A or BPA), in which Y isisopropylidene and A¹ and A² are each p-phenylene. Depending upon themolar excess of resorcinol moiety present in the reaction mixture, R⁵ inthe carbonate blocks may at least partially comprise resorcinol moiety.In other words, in some embodiments of the invention carbonate blocks ofFormula X may comprise a resorcinol moiety in combination with at leastone other dihydroxy-substituted aromatic hydrocarbon.

Diblock, triblock, and multiblock copolyestercarbonates are encompassedin the present invention. The chemical linkages between blockscomprising resorcinol arylate chain members and blocks comprisingorganic carbonate chain members may comprise at least one of

(a) an ester linkage between a suitable dicarboxylic acid residue of anarylate moiety and an —O—R⁵—O— moiety of an organic carbonate moiety,for example as typically illustrated in Formula XII, wherein R⁵ is aspreviously defined:

and (b) a carbonate linkage between a diphenol residue of a resorcinolarylate moiety and a C═O)—O— moiety of an organic carbonate moiety asshown in Formula XIII, wherein R and n are as previously defined:

The presence of a significant proportion of ester linkages of the type(a) may result in undesirable color formation in thecopolyestercarbonates. Although the invention is not limited by theory,it is believed that color may arise, for example, when R⁵ in Formula XIIis bisphenol A and the moiety of Formula XII undergoes Friesrearrangement during subsequent processing and/or light-exposure. In oneembodiment the copolyestercarbonate is substantially comprised of adiblock copolymer with a carbonate linkage between resorcinol arylateblock and an organic carbonate block. In another embodiment thecopolyestercarbonate is substantially comprised of a triblockcarbonate-ester-carbonate copolymer with carbonate linkages between theresorcinol arylate block and organic carbonate end-blocks.

Copolyestercarbonates with at least one carbonate linkage between athermally stable resorcinol arylate block and an organic carbonate blockare typically prepared from resorcinol arylate-containing oligomersprepared by various embodiments of the invention and containing in oneembodiment at least one and in another embodiment at least twohydroxy-terminal sites. Said oligomers typically have weight averagemolecular weight in one embodiment of about 10,000 to about 40,000, andin another embodiment of about 15,000 to about 30,000. Thermally stablecopolyestercarbonates may be prepared by reacting said resorcinolarylate-containing oligomers with phosgene, at least one chain-stopper,and at least one dihydroxy-substituted aromatic hydrocarbon in thepresence of a catalyst such as a tertiary amine.

It is believed that the weatherability and certain other beneficialproperties of the polymers comprising resorcinol arylate polyester chainmembers of the invention are attributable, at least in part, to theoccurrence of thermally or photochemically induced Fries rearrangementof arylate blocks to yield o-hydroxybenzophenone moieties or analogsthereof which serve as stabilizers to UV radiation. More particularly,at least a portion of resorcinol arylate polyester chain members canrearrange to yield chain members with at least one hydroxy group orthoto at least one ketone group. Such rearranged chain members aretypically o-hydroxybenzophenone-type chain members comprising one ormore of the following structural moieties

wherein R and n are as previously defined. Theo-hydroxybenzophenone-type chain members resulting from rearrangement ofresorcinol arylate chain members can be present in resorcinol arylatepolyesters and in resorcinol arylate polyester-containing copolymers,including resorcinol arylate-containing copolyestercarbonates andresorcinol arylate-containing copolyesters containing soft-blocks. It isalso contemplated to introduce moieties of the types illustrated inFormulas XIV, XV, and XVI via synthesis and polymerization ofappropriate monomers in both homopolymers and copolymers by the methodof the present invention. In one embodiment the present inventionprovides thermally stable polyesters, copolyestercarbonates, andcopolyesters comprising structural units represented by Formulas III andXIV, wherein the molar ratio of structural units represented by FormulaIII to structural units represented by Formula XIV ranges in oneembodiment from about 99:1 to about 1:1, and in another embodiment fromabout 99:1 to about 80:20.

The polymers and copolymers comprising thermally stable resorcinolarylate polyester chain members may also be employed in blends with atleast one other polymer, especially polycarbonates (hereinaftersometimes designated “PC”), polyesters, copolyestercarbonates,polyarylates, polyetherimides, polyphenylene ethers, and additionpolymers. Related blends are disclosed in commonly owned U.S. Pat. No.6,143,839.

The polycarbonates in the blend compositions of the invention are, forthe most part, similar in molecular structure to the carbonate blocks ofthe block copolyestercarbonate as described hereinabove, withbisphenol-A homo- and copolycarbonates generally being preferred in someembodiments. Polyesters are illustrated by poly(alkylenedicarboxylates), especially poly(ethylene terephthalate) (hereinaftersometimes designated “PET”), poly(1,4-butylene terephthalate)(hereinafter sometimes designated “PBT”), poly(trimethyleneterephthalate) (hereinafter sometimes designated “PTT”), poly(ethylenenaphthalate) (hereinafter sometimes designated “PEN”), poly(butylenenaphthalate) (hereinafter sometimes designated “PBN”),poly(cyclohexanedimethanol terephthalate),poly(cyclohexanedimethanol-co-ethylene terephthalate) (hereinaftersometimes designated “PETG”), andpoly(1,4-cyclohexanedimethyl-1,4-cyclohexanedicarboxylate) (hereinaftersometimes designated “PCCD”), and especially poly(alkylenearenedioates), with poly(ethylene terephthalate) and poly(1,4-butyleneterephthalate) being preferred in some embodiments.

Copolyestercarbonates may also be used in blends with polymerscomprising resorcinol arylate polyester chain members. Such copolymerscomprise, in addition to the organic carbonate units, ester units suchas isophthalate and/or terephthalate. The copolyestercarbonates whichfind use in the blends of the instant invention and the methods fortheir preparation are well known in the art as disclosed in, forexample, U.S. Pat. Nos. 3,030,331; 3,169,121; 3,207,814; 4,194,038;4,156,069; 4,238,596; 4,238,597; 4,487,896; and 4,506,065.

Polyarylates that may be employed in blends include those known in theart. They often comprise structural units derived from aromaticdihydroxy compounds and aromatic dicarboxylic acid compounds describedherein as suitable for preparation of polycarbonates, polyesters, andcopolyestercarbonates. In various embodiments polyarylates comprisethose with structural units comprising the 1,3-dihydroxybenzene moietypresent in the arylate blocks of the copolyestercarbonates, those withstructural units comprising any organic dihydroxy compound added in thecarbonate block formation step in synthesis of saidcopolyestercarbonates, and those with structural units comprising bothof the aforementioned dihydroxy moieties. Illustrative examples includepolyarylates comprising terephthalate and/or isophthalate structuralunits in combination with one or more of unsubstituted resorcinol,substituted resorcinol, and bisphenol A. The polyetherimide resinsuseful with the present invention are generically known compounds whosepreparation and properties are described in U.S. Pat. Nos. 3,803,085 and3,905,942.

Suitable addition polymers include homopolymers and copolymers,especially homopolymers of alkenylaromatic compounds, such aspolystyrene, including syndiotactic polystyrene, and copolymers ofalkenylaromatic compounds with ethylenically unsaturated nitriles, suchas acrylonitrile and methacrylonitrile; dienes, such as butadiene andisoprene; and/or acrylic monomers, such as ethyl acrylate. These lattercopolymers include the ABS (acrylonitrile-butadiene-styrene) and ASA(acrylonitrile-styrene-alkyl acrylate) copolymers.

In another embodiment the invention encompasses blends of polymersand/or copolymers comprising thermally stable resorcinol arylatepolyester chain members with at least two other polymers. Said at leasttwo other polymers may comprise miscible, immiscible, and compatibilizedblends including, but not limited to, PC/ABS, PC/ASA, PC/PBT, PC/PET,PC/polyetherimide, polyester/polyetherimide, polyphenyleneether/polystyrene, polyphenylene ether/polyamide, and polyphenyleneether/polyester.

The blend compositions of the invention may be prepared by suchconventional operations as solvent blending and melt blending. In someembodiments blend preparation is by melt blending, illustrative examplesof which include extrusion. The blends may additionally containart-recognized additives including, but not limited to, pigments, dyes,impact modifiers, UV screeners, UV absorbers, flame retardants, fillers,stabilizers, heat stabilizers, color stabilizers, flow aids, esterinterchange inhibitors, and mold release agents. It is intended that theblend compositions include simple physical blends and any reactionproducts thereof, as illustrated, for example, bypolyester-polycarbonate transesterification products.

Proportions of the polymers comprising resorcinol arylate polyesterchain members in such blends are determined chiefly by the resultingproportions of arylate blocks, which most often comprise the activeweatherability-improving entities, typical proportions providing about10-50% by weight of arylate blocks in the blend. In blends where somedegree of incompatibility may exist between the polymers comprisingresorcinol arylate polyester chain members of the invention and thepolycarbonates, polyesters, or addition polymers with which they may becombined, said blends are sometimes not fully transparent. However,transparent blends may often be prepared, if desired, by adjusting thelength of the arylate blocks in the polymers comprising resorcinolarylate polyester chain members. The other properties of said blends aregenerally excellent.

Compositions comprising resorcinol arylate polyester chain members madeby various embodiments of the method of the invention typically havesignificantly lower color, both before and after thermal processing,than related compositions made by melt methods, interfacial methods, andsolution methods of the prior art. In particular, melt methods typicallyprovide resorcinol arylate polyester with tan to dark brown color whilethe present interfacial method provides very lightly colored oressentially colorless polyester. The present compositions may be used invarious applications, especially those involving outdoor use andstorage, and hence requiring resistance to weathering. Their lighttransmitting properties are often similar to those of polycarbonates.Thus, they are often substantially transparent and colorless, and mayoften be employed as substitutes for polycarbonates in the fabricationof transparent sheet material when improved weatherability is mandated.

In another embodiment the present invention comprises multilayerarticles comprising a substrate layer comprising at least onethermoplastic polymer, thermoset polymer, cellulosic material, glass,ceramic, or metal, and at least one coating layer thereon, said coatinglayer comprising at least one polymer comprising structural unitsderived from at least one 1,3-dihydroxybenzene moiety and at least onearomatic dicarboxylic acid moiety and prepared by methods embodied inthe present invention. In the present context a multilayer article isone containing at least two layers. In various embodiments a coatinglayer comprises at least one thermally stable polymer comprisingresorcinol arylate polyester chain members substantially free ofanhydride linkages linking at least two mers of the polymer chain.Optionally, the multilayer articles may further comprise an interlayer,for example an adhesive interlayer, between any substrate layer and anythermally stable polymer coating layer. Multilayer articles of theinvention include, but are not limited to, those which comprise asubstrate layer and a coating layer of said thermally stable polymer;those which comprise a substrate layer with a coating layer of saidthermally stable polymer on each side of said substrate layer; and thosewhich comprise a substrate layer and at least one coating layer of saidthermally stable polymer with at least one interlayer between asubstrate layer and a coating layer. Any interlayer may be transparent,translucent, or opaque, and/or may contain an additive, for example acolorant or decorative material such as metal flake. If desired, anoverlayer may be included over the coating layer of thermally stablepolymer, for example to provide abrasion or scratch resistance. Thesubstrate layer, coating layer of thermally stable polymer, and anyinterlayers or overcoating layers are often in contiguous superposedcontact with one another.

Within the context of the present invention it should be understood thatany coating layer comprising a thermally stable polymer comprisingresorcinol arylate polyester chain members may also include polymercomprising o-hydroxybenzophenone or analogous chain members resultingfrom Fries rearrangement of said resorcinol arylate chain members, forexample after exposure of said coating layer to UV-light. Typically, apreponderance of any polymer comprising o-hydroxybenzophenone oranalogous chain members will be on that side or sides of said coatinglayer exposed to UV-light and will overlay in a contiguous superposedlayer or layers that polymer comprising unrearranged resorcinol arylatechain members. If it is worn away or otherwise removed, polymercomprising o-hydroxybenzophenone or analogous chain members is capableof regenerating or renewing itself from the resorcinolarylate-containing layer or layers, thus providing continuous protectionfor any UV-light sensitive layers.

It has been unexpectedly discovered that the presence of at least onestabilizer additive in a coating layer comprising resorcinol arylatepolyester chain members may have a beneficial effect on color despitethe fact that polymers comprising resorcinol arylate polyester chainmembers and their Fries rearrangement products themselves protectagainst photoyellowing. In the present context a stabilizer additive isan additive which provides one or both of lower initial color oradditional resistance to weathering, as measured for example by initialyellowness index (YI), or by resistance to yellowing and change incolor, when compared to a similar coating without at least onestabilizer additive. In a particular embodiment the stabilizer additivecomprises at least one auxiliary color stabilizer additive. In anotherparticular embodiment the stabilizer additive comprises at least oneauxiliary light stabilizer additive. In one embodiment the presence ofat least one auxiliary UV absorber as stabilizer additive providesadditional resistance to weathering, for example as measured by initialyellowness index (YI), or resistance to yellowing and change in color,when compared to a similar coating without at least one auxiliary UVabsorber. Since resorcinol arylate-comprising polymers generate UVabsorber in situ, it is unexpected that the addition of auxiliary UVabsorber would affect the amount of color or yellowness generated.

In various embodiments stabilizer additives include those known in theart. For example, illustrative UV absorbers include, but are not limitedto, hydroxybenzophenones, hydroxybenzotriazoles, hydroxybenzotriazines,cyanoacrylates, oxanilides, and benzoxazinones. Illustrative UVabsorbers also include nano-size inorganic materials such as titaniumoxide, cerium oxide, and zinc oxide, all with particle size less thanabout 100 nanometers. Illustrative examples of stabilizer additives alsoinclude carbodiimides, such as bis-(2,6-diisopropylphenyl)carbodiimideand polycarbodiimides; hindered amine light stabilizers; hinderedphenols; phosphites and phosphorous acid. Such stabilizer additives areknown in the art and are disclosed in standard reference works such as“Plastics Additives Handbook”, 5th edition, edited by H. Zweifel, HanserPublishers. In some embodiments mixtures of stabilizer additives areparticularly effective, especially mixtures of the abovementionedstabilizer additives.

The amount of any stabilizer additive employed is in one embodiment in arange between about 0.0005 wt. % and 10 wt. %, in another embodiment ina range between about 0.001 wt. % and about 10 wt. %, in anotherembodiment in a range between about 0.04 wt. % and about 8 wt. %, inanother embodiment in a range between about 0.1 wt. % and about 6 wt. %,in another embodiment in a range between about 0.2 wt. % and about 5 wt.%, in another embodiment in a range between about 0.5 wt. % and about 5wt. %, and in still another embodiment in a range between about 1 wt. %and about 5 wt. % based on the weight of resorcinol arylate polymer in acoating layer. A stabilizer additive may be combined with coating layerusing known methods. In one embodiment stabilizer additive is at leastpartially dissolved in a solution with components of a coating layer,and a film of coating layer comprising stabilizer additive is solventcast. In another embodiment stabilizer additive is at least partiallydissolved in a solution and impregnated from said solution into solid orat least partially solid coating layer. In still another embodimentstabilizer additive is combined with coating layer in a melt method suchas co-extrusion. If desired, the stabilizer additive may be combinedwith coating layer in the form of a solution of stabilizer additive, forexample in water or organic solvent. In one embodiment an aqueoussolution of phosphorous acid is employed as stabilizer additive.

The multilayer articles typically have outstanding initial gloss,improved initial color, weatherability, impact strength, and resistanceto organic solvents encountered in their final applications. Saidarticles may also be recyclable by reason of the compatibility of thediscrete layers therein.

The material of the substrate layer in the articles of this inventionmay be at least one thermoplastic polymer, whether addition orcondensation prepared. Thermoplastic polymers include, but are notlimited to, polycarbonates, particularly aromatic polycarbonates,polyacetals, polyarylene ethers, polyphenylene ethers, polyarylenesulfides, polyphenylene sulfides, polyimides, polyamideimides,polyetherimides, polyetherketones, polyaryletherketones,polyetheretherketones, polyetherketoneketones, polyamides, polyesters,liquid crystalline polyesters, polyetheresters, polyetheramides,polyetheramides, and polyestercarbonates (other than those employed forthe coating layer, as defined hereinafter). In some embodimentspolycarbonates and polyesters are preferred. A substrate layer mayadditionally contain art-recognized additives including, but not limitedto, colorants, pigments, dyes, impact modifiers, stabilizers, colorstabilizers, heat stabilizers, UV screeners, UV absorbers, flameretardants, fillers, flow aids, ester interchange inhibitors, and moldrelease agents.

Suitable polycarbonates include homopolycarbonates comprising structuralunits of the type described for the organic carbonate blocks in thecopolyestercarbonates of the invention. In some embodiments thepolycarbonates are bisphenol A homo- and copolycarbonates. In variousembodiments the weight average molecular weight of the initialpolycarbonate ranges from about 5,000 to about 100,000; in otherembodiments the weight average molecular weight of the initialpolycarbonate ranges from about 25,000 to about 65,000.

The polycarbonate substrate may also be a copolyestercarbonate (otherthan that copolyestercarbonate employed for the coating layer as definedhereinafter). Such copolymers typically comprise, in addition to theorganic carbonate units, ester units such as isophthalate and/orterephthalate. The copolyestercarbonates which find use as substrates inthe instant invention and the methods for their preparation are wellknown in the art as disclosed in, for example, U.S. Pat. Nos. 3,030,331;3,169,121; 3,207,814; 4,194,038; 4,156,069; 4,238,596; 4,238,597;4,487,896; and 4,506,065.

Polyester substrates include, but are not limited to, poly(alkylenedicarboxylates), especially poly(ethylene terephthalate),poly(1,4-butylene terephthalate), poly(trimethylene terephthalate),poly(ethylene naphthalate), poly(butylene naphthalate),poly(cyclohexanedimethanol terephthalate),poly(cyclohexanedimethanol-co-ethylene terephthalate), andpoly(1,4-cyclohexanedimethyl-1,4-cyclohexanedicarboxylate). Alsoincluded are polyarylates as described hereinabove, illustrativeexamples of which include those comprising structural units derived frombisphenol A, terephthalic acid, and isophthalic acid.

Suitable addition polymer substrates include homo- and copolymericaliphatic olefin and functionalized olefin polymers (which arehomopolymers and copolymers comprising structural units derived fromaliphatic olefins or functionalized olefins or both), and their alloysor blends. Illustrative examples include, but are not limited to,polyethylene, polypropylene, thermoplastic polyolefin (“TPO”),ethylene-propylene copolymer, poly(vinyl chloride), poly(vinylchloride-co-vinylidene chloride), poly(vinyl fluoride), poly(vinylidenefluoride), poly(vinyl acetate), poly(vinyl alcohol), poly(vinylbutyral), poly(acrylonitrile), acrylic polymers such as those of(meth)acrylamides or of alkyl(meth)acrylates such as poly(methylmethacrylate) (“PMMA”), and polymers of alkenylaromatic compounds suchas polystyrenes, including syndiotactic polystyrene. In some embodimentsthe preferred addition polymers are polystyrenes and especially theso-called ABS and ASA copolymers, which may contain thermoplastic,non-elastomeric styrene-acrylonitrile side chains grafted on anelastomeric base polymer of butadiene and alkyl acrylate, respectively.

Blends of any of the foregoing polymers may also be employed assubstrates. Typical blends include, but are not limited to, thosecomprising PC/ABS, PC/ASA, PC/PBT, PC/PET, PC/polyetherimide,PC/polysulfone, polyester/polyetherimide, PMMA/acrylic rubber,polyphenylene ether-polystyrene, polyphenylene ether-polyamide orpolyphenylene ether-polyester. Although the substrate layer mayincorporate other thermoplastic polymers, the above-describedpolycarbonates and/or addition polymers often constitute the majorproportion thereof.

The substrate layer in the multilayer articles of this invention mayalso comprise at least one of any thermoset polymer. Suitable thermosetpolymer substrates include, but are not limited to, those derived fromepoxys, cyanate esters, unsaturated polyesters, diallylphthalate,acrylics, alkyds, phenol-formaldehyde, novolacs, resoles, bismaleimides,PMR resins, melamine-formaldehyde, urea-formaldehyde, benzocyclobutanes,hydroxymethylfurans, and isocyanates. In one embodiment of the inventionthe thermoset polymer substrate comprises a RIM material. In anotherembodiment of the invention the thermoset polymer substrate furthercomprises at least one thermoplastic polymer, such as, but not limitedto, polyphenylene ether, polyphenylene sulfide, polysulfone,polyetherimide, or polyester. Said thermoplastic polymer is typicallycombined with thermoset monomer mixture before curing of said thermoset.

In one embodiment of the invention a thermoplastic or thermosetsubstrate layer also incorporates at least one filler and/or pigment.Illustrative extending and reinforcing fillers, and pigments includesilicates, zeolites, titanium dioxide, stone powder, glass fibers orspheres, carbon fibers, carbon black, graphite, calcium carbonate, talc,mica, lithopone, zinc oxide, zirconium silicate, iron oxides,diatomaceous earth, calcium carbonate, magnesium oxide, chromic oxide,zirconium oxide, aluminum oxide, crushed quartz, calcined clay, talc,kaolin, asbestos, cellulose, wood flour, cork, cotton and synthetictextile fibers, especially reinforcing fillers such as glass fibers,carbon fibers, and metal fibers, as well as colorants such as metalflakes, glass flakes and beads, ceramic particles, other polymerparticles, dyes and pigments which may be organic, inorganic ororganometallic. In another embodiment the invention encompassesmultilayer articles comprising a filled thermoset substrate layer suchas a sheet-molding compound (SMC).

The substrate layer may also comprise at least one cellulosic materialincluding, but not limited to, wood, paper, cardboard, fiber board,particle board, plywood, construction paper, Kraft paper, cellulosenitrate, cellulose acetate butyrate, and like cellulosic-containingmaterials. The invention also encompasses blends of at least onecellulosic material and either at least one thermoset polymer(particularly an adhesive thermoset polymer), or at least onethermoplastic polymer (particularly a recycled thermoplastic polymer,such as PET or polycarbonate), or a mixture of at least one thermosetpolymer and at least one thermoplastic polymer.

Multilayer articles encompassed by the invention also include thosecomprising at least one glass layer. Typically any glass layer is asubstrate layer, although multilayer articles comprising a thermallystable polymer coating layer interposed between a glass layer and asubstrate layer are also contemplated. Depending upon the nature ofcoating and glass layers, at least one adhesive interlayer may bebeneficially employed between any glass layer and any thermally stablepolymer coating layer. The adhesive interlayer may be transparent,opaque or translucent. For many applications it is preferred that theinterlayer be optically transparent in nature and generally have atransmission of greater than about 60% and a haze value less than about3% with no objectionable color.

Metal articles exposed to UV-light may exhibit tarnishing and otherdetrimental phenomena. In another embodiment the invention encompassesmultilayer articles comprising at least one metal layer as substratelayer. Representative metal substrates include those comprising brass,aluminum, magnesium, chrome, iron, steel, copper, and other metals oralloys or articles containing them, which may require protection fromUV-light or other weather phenomena. Depending upon the nature ofcoating and metal layers, at least one adhesive interlayer may bebeneficially employed between any metal layer and any thermally stablepolymer coating layer.

Also present in the articles of the invention is at least one coatinglayer comprising at least one polymer comprising structural unitsderived from at least one 1,3-dihydroxybenzene moiety and at least onearomatic dicarboxylic acid moiety prepared by methods embodied in thepresent invention. In various embodiments, suitable coating layerscomprise polymers comprising thermally stable resorcinol arylatepolyester chain members. In other embodiments suitable coating layerscomprise resorcinol arylate polyesters, copolyesters (particularly thosecontaining soft-blocks), copolyestercarbonates, and mixtures thereof.Copolyestercarbonates, when used in both substrate layer and in coatinglayer, are different from each other in molecular structure. Morespecifically, when the coating layer contains copolyestercarbonate withresorcinol arylate polyester blocks, then any ester blocks in thesubstrate copolyestercarbonate layer will typically be derived from thesame divalent organic radical as contained in the carbonate blocks.

It is also within the scope of the invention for other polymers to bepresent which are miscible in at least some proportions with a polymercoating layer comprising at least one thermally stable polymercomprising structural units derived from at least one1,3-dihydroxybenzene moiety and at least one aromatic dicarboxylic acidmoiety. Illustrative examples of at least partially miscible polymersinclude polyetherimide and polyesters such as PBT, PET, PTT, PEN, PBN,PETG, PCCD, and bisphenol A polyarylate. In one embodiment the coatinglayer polymer consists essentially of thermally stable resorcinolarylate polyesters, copolyesters, or copolyestercarbonates.

Another aspect of the invention is a method for preparing a multilayerarticle which comprises applying at least one thermally stable coatinglayer to a second layer, said second layer comprising at least onethermoplastic polymer, thermoset polymer, cellulosic material, glass, ormetal, and said coating layer comprising at least one polymer comprisingstructural units derived from at least one 1,3-dihydroxybenzene moietyand at least one aromatic dicarboxylic acid moiety, the polymer beingsubstantially free of anhydride linkages linking at least two mers ofthe polymer chain.

In one embodiment of the invention, at least one thermally stablecoating layer is applied to a second layer, which may be the substratelayer or at least one intermediate layer ultimately to be disposedbetween the coating and substrate layers. An intermediate layer maycomprise any of the materials suitable for use as the substrate orcoating layer, and may further contain fillers and colorants such asdescribed hereinabove. When necessary, it may be specifically chosen soas to provide good adhesion between substrate and coating layers.Colorants of the previously described types may also be present in thecoating layer.

In one embodiment application of the at least one coating layer may beperformed by solvent-casting. In another embodiment application of saidcoating layer comprises fabrication of a separate sheet thereof followedby application to the second layer, or by simultaneous production ofboth layers, typically in a melt process. Thus, there may be employedsuch methods as thermoforming, compression molding, co-injectionmolding, coextrusion, overmolding, blow molding, multi-shot injectionmolding and placement of a film of the coating layer material on thesurface of the second layer followed by adhesion of the two layers,typically in an injection molding apparatus; e.g., in-mold decoration,or in a hot-press. These operations may be conducted underart-recognized conditions.

It is also within the scope of the invention to apply a structurecomprising the coating layer and the second layer to a third, substratelayer, which may be, for example, of a thermoplastic, thermoset, orcellulosic material similar or identical to that of the second layer butdifferent from that of the coating layer. This may be achieved, forexample, by charging an injection mold with the structure comprising thecoating layer and the second layer and injecting the substrate sheetmaterial behind it. By this method, in-mold decoration and the like arepossible. Both sides of the substrate layer may receive the otherlayers, though in some embodiments it may be preferred to apply them toonly one side.

The thicknesses of the various layers in multilayer articles of thisinvention are most often as follows:

substrate—at least about 125μ (microns), or at least about 250μ, or atleast about 400μ,

coating—about 2-2,500, or about 10-250, or about 50-175μ,

second material, if any—about 2-2,500, or about 10-250, or about50-175μ,

total—at least about 125μ, or at least about 250μ, or at least about400μ.

The articles of this invention are typically characterized by the usualbeneficial properties of the substrate layer, in addition toweatherability as may be evidenced by such properties as improvedinitial gloss, improved initial color, improved resistance toultraviolet radiation and maintenance of gloss, improved impactstrength, and resistance to organic solvents encountered in their finalapplications. Depending upon such factors as the coating layer/substratecombination, the multilayer articles may possess recycling capability,which makes it possible to employ the regrind material as a substratefor further production of articles of the invention.

Multilayer articles which can be made which comprise thermally stablepolymers comprising resorcinol arylate polyester chain members includeaircraft, automotive, truck, military vehicle (including automotive,aircraft, and water-borne vehicles), scooter, and motorcycle exteriorand interior components, including panels, quarter panels, rockerpanels, trim. fenders, doors, decklids, trunklids, hoods, bonnets,roofs, bumpers, fascia, grilles, mirror housings, pillar appliques,cladding, body side moldings, wheel covers, hubcaps, door handles,spoilers, window frames, headlamp bezels, headlamps, tail lamps, taillamp housings, tail lamp bezels, license plate enclosures, roof racks,and running boards; enclosures, housings, panels, and parts for outdoorvehicles and devices; enclosures for electrical and telecommunicationdevices; outdoor furniture; aircraft components; boats and marineequipment, including trim, enclosures, and housings; outboard motorhousings; depth finder housings, personal water-craft; jet-skis; pools;spas; hot-tubs; steps; step coverings; building and constructionapplications such as glazing, roofs, windows, floors, decorative windowfurnishings or treatments; treated glass covers for pictures, paintings,posters, and like display items; optical lenses; ophthalmic lenses;corrective ophthalmic lenses; implantable ophthalmic lenses; wallpanels, and doors; counter tops; protected graphics; outdoor and indoorsigns; enclosures, housings, panels, and parts for automatic tellermachines (ATM); enclosures, housings, panels, and parts for lawn andgarden tractors, lawn mowers, and tools, including lawn and gardentools; window and door trim; sports equipment and toys; enclosures,housings, panels, and parts for snowmobiles; recreational vehicle panelsand components; playground equipment; shoe laces; articles made fromplastic-wood combinations; golf course markers; utility pit covers;computer housings; desk-top computer housings; portable computerhousings; lap-top computer housings; palm-held computer housings;monitor housings; printer housings; keyboards; FAX machine housings;copier housings; telephone housings; phone bezels; mobile phonehousings; radio sender housings; radio receiver housings; lightfixtures; lighting appliances; network interface device housings;transformer housings; air conditioner housings; cladding or seating forpublic transportation; cladding or seating for trains, subways, orbuses; meter housings; antenna housings; cladding for satellite dishes;coated helmets and personal protective equipment; coated synthetic ornatural textiles; coated photographic film and photographic prints;coated painted articles; coated dyed articles; coated fluorescentarticles; coated foam articles; and like applications. The inventionfurther contemplates additional fabrication operations on said articles,such as, but not limited to, molding, in-mold decoration, baking in apaint oven, lamination, and/or thermoforming.

The invention is illustrated by the following, non-limiting examples.All parts are by weight unless otherwise designated. Molecular weightvalues for polymeric samples were determined by gel permeationchromatography (GPC) using 3% isopropanol/chloroform eluent at 0.75milliliters (ml) per minute (min) on a Polymer Labs Mixed C sizeexclusion column held at 35° C., and calibrated using polystyrenestandards, and analyzed with Turbogel software.

EXAMPLE 1

This example illustrates the preparation of a thermally stableresorcinol arylate polyester with both iso- and terephthalate units. Toa one liter, five neck, Morton flask blanketed with nitrogen andequipped with a mechanical stirrer, pH electrode, reflux condenser, twopressure equalizing addition funnels, was charged resorcinol (21.8 grams[g]; 0.198 moles [mol]), resorcinol monobenzoate capping agent (1.07 g;2.5 mole %), triethylamine (0.274 ml; 1 mole %), dichloromethane (150ml), and water (100 ml). One addition funnel was charged with sodiumhydroxide pellets (16.84 g; 0.42 mol)and water (32 ml), while a solutionof isophthaloyl dichloride (20.3 g; 0.1 mol), terephthaloyl dichloride(20.3 g; 0.1 mol), and dichloromethane (150 ml) was added to the second.The pH of the reaction mixture was adjusted to 7.5 with sodium hydroxideprior to the addition of acid chloride solutions, which were added over6 minutes. The pH of the reaction was maintained between 7.25 and 7.75for the first ten minutes of reaction. At 11 minutes the reaction the pHwas raised to about 10 with the addition of sodium hydroxide and heldfor an additional 10 minutes. The stirring was stopped and the aqueouslayer was removed. The resulting gray organic layer was washed with 1Nhydrochloric acid, 0.1N hydrochloric acid, water (three times), and thepolymer isolated by precipitation into boiling water yielding a white,fibrous material which was dried in vacuum at 110° C. overnight. Theisolated polymer was the desired resorcinol arylate polyester.

Control Example 1

A polyester of resorcinol with a mixture of iso- and terephthalate wasprepared in a blender according to the interfacial method of U.S. Pat.No. 3,460,961. The isolated polymer had weight average molecular weightof about 289,000. The procedure was modified by addition of 4 mole %chain-stopper (phenol), resulting in polymer with weight averagemolecular weight of about 51,000.

Control Example 2

A polyester of resorcinol with a mixture of iso- and terephthalate wasprepared according to the solution method of Cohen et al., Journal ofPolymer Science: Part A-1, vol. 9, 3263-3299 (1971). To a one-liter,three neck, round bottomed flask equipped with a mechanical stirrer andan addition funnel were charged isophthaloyl dichloride (5.076 g, 25millimoles [mmol]), terephthaloyl dichloride (5.076 g, 25 mmol),resorcinol (5.506 g, 50 mmol), and tetrahydrofuran (200 ml) dried bydistillation from sodium and benzophenone. Polymerization was initiatedby dropwise addition of a stoichiometric amount of triethylamine (10.12g, 10 mmol) over 30 minutes. The mixture then was stirred for 3 hours atroom temperature. Triethylamine hydrochloride was removed from thereaction mixture by filtration. The filtrate was slowly poured intomethanol (500 ml) in a blender. The precipitated polymer was washed withhot water and dried in a vacuum oven. The isolated polymer had weightaverage molecular weight of about 47,000.

EXAMPLES 2-11

These examples illustrate the preparation of hydroxy-terminatedresorcinol iso/terephthalate oligomers. Into a 1 liter Morton flaskequipped with a mechanical stirrer, pH electrode, condenser, and twoaddition tubes connected to metering pumps were charged resorcinol(12.11 g, 0.11 mol), water (18 ml), methylene chloride (200 ml), andtriethylamine (140 to 560 microliters, 1 to 4 mol % based on acidchlorides). The mixture was stirred at 500 rpm. A two-step additionprofile was used for the delivery of acid chloride solution and basesolution. In the first step, a majority of base (60 to 80% out of totalbase amount of 17.5 ml of 33% aqueous sodium hydroxide solution) and thewhole acid chloride solution (70 ml solution of isophthaloyl dichloride(10.15 g, 0.05 mol) and terephthaloyl dichloride (10.15 g, 0.05 mol) inmethylene chloride) were added at constant rates, and the remaining basewas added in the second step at continuously decreasing rate. The basewas pumped from graduated burets and the amount was checked every 30seconds in order to control the stoichiometry. The pH varied betweenabout 3.5 and about 8. The length of the first step was varied from 7 to13 minutes with the total step 1 and step 2 time constant at 25 minutes.The reaction mixture was further stirred for 30 minute total reactiontime. The reaction conditions and weight average molecular weights ofthe isolated polymers are shown in Table 1.

TABLE 1 % Base Added in 1st Base Addition mol % Oligomer Example Steptime (min.) triethylamine Mw^(a) 2 60 7 1 27.3 3 60 7 4 26.9 4 60 13 424.5 5 60 13 1 26 6 70 10 2.5 28.3 7 70 10 2.5 23 8 80 7 4 28.4 9 80 7 130.8 10  80 13 4 29.5 11  80 13 1 30.4 ^(a)times 10⁻³

A sample of each polymer was analyzed for anhydride content by treatmentin solution with diisobutylamine. Polymers prepared using 4 mol %triethylamine showed greater than 95% retention of weight averagemolecular weight.

EXAMPLES 12-28

The procedure of Examples 2-11 was repeated except that in someexperiments 13 to 15 mol % total excess of resorcinol was used. In someexperiments a small amount of capping agent (1 mol % phenol) was added.In some cases, the reaction mixture was heated externally to a refluxingpoint at 3 minutes. The reaction conditions and weight average molecularweights of the isolated polymers are shown in Table 2.

TABLE 2 mol % Initial % Mw Example triethylamine Comments^(a) Reflux^(b)Mw^(c) Retention^(d) 12 4 1% PhOH Y 19.5 99 13 4 15% excess N 19.9 100Rs 14 4 0.5% PhOH N 21.6 99.5 15 4 15% excess Y 21.8 96.6 Rs 16 4 1%PhOH N 21.9 99.3 17 4 1% PhOH Y 22.2 97.7 18 4 N 22.3 96.1 19 4 13%excess N 22.4 97.7 Rs 20 4 1% PhOH Y 22.4. 96.4 21 4 1% PhOH Y 22.5 9322 4 1% PhOH N 22.7 97.8 23 4 0.5 PhCOCl N 24.6 99 24 2.5 1% PhOH Y 24.797.2 25 4 N 24.8 96.7 26 4 Y 25.3 98 27 4 N 26.6 97.7 28 3 Y 30.3 100^(a)PhOH (phenol); Rs (resorcinol); PhCOCl (benzoyl chloride) ^(b)Y(Yes); N (No) ^(c)times 10⁻³ ^(d)following treatment withdiisobutylamine in solution

EXAMPLES 29-46

The procedure of Examples 2-11 was repeated except that a portion oftertiary amine was added following addition of dicarboxylic aciddichloride to resorcinol moiety. A total of 4 mol % tertiary amine(40000 ppm; based on moles acid chlorides) was added. The reactionconditions and weight average molecular weights of the isolated polymersare shown in Table 3. Example 46 is a control experiment in which allthe tertiary amine was present at the beginning of the reaction beforeaddition of dicarboxylic acid dichloride to resorcinol moiety.

TABLE 3 % Base Base TEA added Exam- Added in Addition initially Initial% Mw ple 1st Step time (min.) (ppm) MW^(a) Retention^(b) 29 80 7 50 29.396.5 30 80 7 10 23.1 86.8 31 80 7 10 22.2 98.5 32 80 7 50 29.4 97.4 3396 7 10 32.7 94.3 34 96 7 50 34.4 92.5 35 88 10 30 26.5 99.4 36 88 10 3025.6 101 37 80 13 50 25.9 95.9 38 80 13 10 25.2 96.6 39 96 13 50 29.490.2 40 96 13 10 22.14 98.59 41 96 13 50 26.7 92.93 42 96 13 10 23.690.5 43 96 16 10 21.6, 22.0 98.8, 98.0 44 96 19 10 24.1, 22.3 95.9, 97.345 64 7 10 21.46, 96.3, 100 23.31 46 96 16 40000 24.7, 23.1 92.7, 94.4^(a)times 10⁻³ ^(b)following treatment with diisobutylamine in solution

EXAMPLE 47

This example illustrates the preparation of a thermally stableresorcinol iso/terephthalate-block-copolycarbonate beginning with thepreparation of hydroxy-terminated resorcinol iso/terephthalate oligomer.To a thirty liter glass reactor equipped with a glass impeller,centrifuge recirculation pump, reflux condenser andpressure-equilibration addition funnel were charged resorcinol (605.6 g,5.5 mol), methyltributylammonium chloride (82.5 g of a 75 wt. % aqueoussolution; 0.275 mol), dichloromethane (6.5 liters), and water (2.5liters). The recirculation pump was turned on and the mixture wasdegassed with nitrogen while stirring. The pH of the aqueous phase wasadjusted to 7 with 50% aqueous sodium hydroxide solution. Reaction wascarried out by adding a solution of acid chlorides (507.5 g each of iso-and terephthaloyl dichlorides; 5.00 moles total in 2.0 liters ofdichloromethane solution) while stirring and simultaneously adding 50%sodium hydroxide solution at such a rate that the pH was maintainedbetween 6 and 8. The acid chlorides were added using a three-stepprogram with the rate of addition declining with each step. A timer wasstarted at the beginning of acid chloride addition. The pH wasmaintained at 8 while adding acid chlorides over 8 minutes using thefollowing protocol: 40% of total acid chlorides was added over the first2 minutes; 30% of total was added over the next 2 minutes; the remaining30% of total was added over the next 4 minutes. The recirculation loopwas running during the entire time.

Following complete addition of acid chlorides, the pH was slowly raisedto 11-12 over two to three minutes, and the reaction mixture was stirredfor 10 minutes. The polymer formed was a hydroxy-terminated oligomerwith weight average molecular weight (Mw) of approximately 20,000.

Bisphenol A (1102 g, 4.83 mol), dichloromethane (4.0 liters),triethylamine (17 ml, 0.12 mol), p-cumyl phenol capping agent (60 g),and water (6.0 liters) were then added and the recirculation loop wasturned on. Phosgene was introduced at pH 7.5-8.5, then increasing slowlyto pH 10-10.5 using a 15% excess over the theoretical amount ofphosgene.

The reaction mixture was separated, the organic phase washed with 1Nhydrochloric acid, 0.1N hydrochloric acid, and twice with water, and thepolymer was isolated by precipitation in methanol. The polymer obtainedwas the desired resorcinol iso/terephthalate-co-BPA polycarbonatecopolymer.

EXAMPLES 48-61

Samples of polymers comprising resorcinol arylate polyester chainmembers were dried in vacuo at 120° C. for 15 hrs. A weighed sample ofabout 25-30 milligrams was placed in a circular die cavity 2 centimeters(cm.) in diameter and covered with a cylindrical piston of the samesize. The die assembly containing the sample was heated in a Carverpress at 290° C. for 5 minutes at 500-4,000 pounds gauge (lbs.g.)pressure, then removed and cooled in chill blocks. The heat treatmentproduced a film about 1 mil in thickness and 2 cm. in diameter.Molecular weights of samples before and after the heat treatment weremeasured by GPC using polystyrene standards. Table 4 shows examples ofmelt stability for resorcinol arylate polyesters prepared using themethod of Example 1 and Control Examples 1 and 2, and for resorcinolarylate-containing copolyestercarbonates prepared using the method ofExample 47. Wt. % resorcinol arylate in the Table refers to theapproximate wt. % resorcinol arylate chain members in the polymer, theremaining mers being organic carbonate mers.

TABLE 4 wt. % % Mw resorcinol % Mw Retention, Retention, Example arylatemelt test amine test^(f) 48^(a) 50 89.4 98 49^(a) 80 84 97.9 50^(a) 5084.8 94 51^(b) 50 98.8 99.5 52^(b) 35 98.7 99.3 53^(a) 100 55 62 54^(a)100 55.9 61 55^(a) 100 45 40 56^(b) 100 87.5 86 57^(b) 100 97.7 99.658^(b) 100 99.5 99 59^(c) 100 12 25 60^(d) 100 46 74 61^(c) 100 77 78^(a)final reaction mixture stirred 5 min at pH 10 ^(b)final reactionmixture stirred 20 min at pH 10-12 ^(c)Control Example 1 ^(d)ControlExample 1 using 4 mole % phenol chain-stopper ^(e)Control Example 2^(f)following treatment with diisobutylamine in solution

EXAMPLE 62

A resorcinol arylate polyester was prepared by the interfacial method ofControl Example 1 except that the organic solvent was dichloromethaneand a capping agent was present. Extrusion of the material gave orangepellets. The polymer had initial weight average molecular weight (Mw) of61,300 and Mw after extrusion of 52,200 (85% retention). A separatesample of material was treated with dibutylamine in solution; the Mw ofthe recovered material was 42,400 (69% retention).

EXAMPLE 63

A resorcinol arylate polyester was prepared by the method of Example 1.Extrusion of the material gave yellowish pellets. The polymer hadinitial Mw of 53,600 and Mw after extrusion of 50,800 (95% retention). Aseparate sample of material was treated with dibutylamine in solution;the Mw of the recovered material was 48,400 (90% retention).

EXAMPLE 64

A resorcinol arylate-containing block copolyester-carbonate with about50% by weight carbonate blocks and 1:1 ratio of isophthalate toterephthalate in the resorcinol arylate blocks was prepared by themethod of Example 47 except that the resorcinol arylate-containingpolyester block was made using the procedure of Control Example 1 usinga capping agent and dichloromethane as the organic solvent. Extrusion ofthe material gave amber pellets. The copolymer had initial Mw of 75,900and Mw after extrusion of 64,500 (85% retention). A separate sample ofmaterial was treated with dibutylamine in solution; the Mw of therecovered material was 73,000 (96% retention).

EXAMPLE 65

A resorcinol arylate-containing block copolyester-carbonate was preparedby the method of Example 47 with about 50% by weight carbonate blocksand 1:1 ratio of isophthalate to terephthalate in the resorcinol arylateblocks. Extrusion of the material gave faintly yellowish pellets. Thecopolymer had initial Mw of 52,300 and Mw after extrusion of 51,700 (99%retention). A separate sample of material was treated with dibutylaminein solution; the Mw of the recovered material was 51,500 (98%retention).

Disks were formed from the resorcinol arylate-containing polymers ofExamples 62-65. The disks were approximately 0.6 millimeters (mm) (0.024inches) thick and 50 mm (2.0 inches) diameter, and were formed frommelt-processed polymer (either pellets, extruded film, or injectionmolded parts) under the following conditions: 2.1 g of melt-processedpolymer were placed in a mold between heated platens of a hydraulicpress and heated at about 200° C. with no applied pressure for 3minutes, then under 4500 lbs.g. pressure for 1 minute, and finally under6500 lbs.g. pressure for 1 minute. The mold was then rapidly cooled inice water and opened to remove the disk.

The disks prepared as described were laminated onto injection-moldedplaques of LEXAN 140 polycarbonate (from General Electric Plastics)containing 2 wt. % of titanium dioxide pigment under the followingconditions to make well-adhered multilayer articles. All materials wereplaced in a heated (60° C.) vacuum desiccator overnight. A disk wasplaced onto an injection molded plaque of polycarbonate 2.5 inchessquare and one-eighth inch thick in a mold between heated platens of ahydraulic press and heated at about 200° C. with no applied pressure for2 minutes, then under 4500 lbs. gauge pressure for 1 minute, and finallyunder 6500 lbs. gauge pressure for 1 minute. All samples were welladhered.

The color of the disks and of the laminated plaques was determined on aGretagMacbeth™ Color-Eye 7000A colorimeter and reported as CIELAB valuesand yellowness index (YI; according to ASTM D1925). Results are shown onTable 5.

TABLE 5 Disks (transmission) Laminate on PC (reflection) Example L* a*b* YI L* a* b* YI 62 90.45 −1.23 15.2 26.01 76.6 3.57 31.74 61.07 6394.73 −0.3 3.61 6.34 86.18 −0.38 14.95 27.4 64 93.82 −0.43 5.4 9.5 84.210.88 20.44 38.27 65 95.52 −0.11 1.31 2.26 91.21 −0.8 6.95 12 unlaminated94.86 −0.52 2.88 4.51 PC

The data show that the disks and multilayer articles formed frommelt-processed resorcinol arylate-containing polymers made by a methodof the invention have much less color and lower yellowness index thanthe respective control blends.

EXAMPLES 66-74

In these Examples all the resorcinol arylate polymers comprisedstructural units derived from resorcinol and a 1:1 mixture of iso- andterephthaloyl dichlorides. The Examples used either a resorcinol arylatepolyester (Polymer A) or a resorcinol arylate block copolymer withbisphenol A polycarbonate (Polymer B with about 30 wt. % carbonateunits, or Polymer C with about 50 wt. % carbonate units). As stabilizeradditives, commercial UV absorbers (“UVA”) available from Cytec Corp.were employed: CYASORB 5411 (UVA 1), CYASORB 531 (UVA 2), and CYASORB1164 (UVA 3). Films were cast from resorcinol arylate-comprising polymerby dissolving 2 grams of the polymer and any auxiliary UV absorber in 8milliliters of chloroform. The solution was drawn onto a glass plateusing 12 mil doctor blade and allowed to dry in air resulting in a filmabout 40 microns thick. The films were laminated onto injection-moldedplaques of LEXAN polycarbonate (from General Electric Plastics)containing 2 wt. % of titanium dioxide pigment under the followingconditions to make multilayer articles. Two layers of these films wereplaced on top of injection molded plaques comprising LEXAN, and theassembly was placed in a Carver press. The sample in the press washeated at about 210° C. with no applied pressure for 2 minutes, under4500 lbs. gauge pressure for 1 minute, and finally under 6500 lbs. gaugepressure for 1 minute. The films were well adhered to the substrates.The samples were exposed to weathering in an Atlas Ci4000 xenon arcweatherometer equipped with borosilicate inner and outer filters at anirradiance of 0.77 watts per square meter at 340 nanometers. Exposureconditions were black panel 63° C., dry bulb 43° C., humidity 30%,continuous illumination. The cycle was 102 minutes light followed by 18minutes with water spray. Samples were evaluated for color on aGretagMacbeth™ Color-Eye 7000A colorimeter with results reported asΔE(ΔE=ΔL²+Δa²+Δb²)^(1/2)) and change in yellowness index (ΔYI; accordingto ASTM D1925). Exposure was measured in kilojoules per square meter ofenergy received at 340 nanometers. Results are shown in Table 6. Theamount of UVA shown was based on total solids.

TABLE 6 UV ΔYI at ΔYI at ΔE at Example Polymer Absorber Initial YI 242kJ/m² 1127 kJ/m² 1127 kJ/m² 66 A none 5.49 11.02 12.76 10.37 67 A 1% UVA1 6.06 8.74 10.57 8.66 68 B none 4.63 9.43 11.62 9.26 69 B 1% UVA 1 4.917.53 9.89 7.92 70 B 5% UVA 1 5.77 4.52 6.92 5.61 71 B 1% UVA 2 5.48 7.219.68 7.65 72 B 1% UVA 3 5.52 7.52 9.84 7.92 73 C none 4.73 8.66 11.809.18 74 C 1% UVA 1 5.08 7.31 9.96 7.87

In each case the use of 1% UVA reduced the amount of yellowing by about15%, while the use of 5% UVA reduced the amount of yellowing by about40%.

EXAMPLES 75-82

In these Examples the resorcinol arylate polymer comprised structuralunits derived from resorcinol and a 1:1 mixture of iso- andterephthaloyl dichlorides. The Examples used a resorcinol arylate blockcopolymer with bisphenol A polycarbonate containing about 15 wt. %carbonate units. As stabilizer additives, commercial stabilizers wereemployed, sometimes in combination with phosphorous acid. Phosphorousacid was employed as a 45 wt. % solution in deionized water. Stabilizeradditives were mixed with block copolymer before extrusion using asingle-screw extruder. The extruded mixture was molded into plaquesabout one-eighth inch thick. The color of the disks was determined andreported as yellowness index (YI; according to ASTM D1925). The resultsare shown in Table 7. The amounts of stabilizer used are reported inparts based on 100 parts resin (phr).

TABLE 7 Exam- Initial ple Stabilizer additive (phr) YI 75 none 17.2 76Bis(2,4-dicumylphenyl)pentaerythritol diphosphite (0.03) 12.9 77Bis(2,4-dicumylphenyl)pentaerythritol diphosphite (0.1) 9.2 78Bis(2,4-dicumylphenyl)pentaerythritol diphosphite (0.1) + deionizedwater (0.1) 79 Bis(2,4-dicumylphenyl)pentaerythritol diphosphite 8.5(0.05) + phosphorous acid (0.005) 80Bis(2,4-dicumylphenyl)pentaerythritol diphosphite 7.1 (0.1) +phosphorous acid (0.005) 81 Bis(2,4-dicumylphenyl)pentaerythritoldiphosphite 7.0 (0.15) + phosphorous acid (0.005) 82Bis(2,4-dicumylphenyl)pentaerythritol diphosphite 6.9 (0.1) +phosphorous acid (0.01)

In each case the addition of phosphite stabilizer alone or incombination with phosphorous acid reduced the initial YI.

EXAMPLES 83

A resorcinol arylate block copolymer with bisphenol A polycarbonate asdescribed in Examples 75-82 was mixed with 0.0005 phr phosphorous acidand 0.1 phr bis(2,4-dicumylphenyl)pentaerythritol diphosphite using themethod described in Examples 75-82. Molded plaques showed YI of 8.3.

EXAMPLE 84

A resorcinol arylate block copolymer with bisphenol A polycarbonate asdescribed in Examples 75-82 was mixed with 0.005 phr phosphorous acidand 0.1 phr tris(2,4-di-tert-butylphenyl)phosphite using the methoddescribed in Examples 75-82. Molded plaques showed YI of 7.4.

EXAMPLE 85

A resorcinol arylate block copolymer with bisphenol A polycarbonate asdescribed in Examples 75-82 was mixed with 0.005 phr phosphorous acid,0.07 phr tris(2,4-di-tert-butylphenyl)phosphite, and 0.03 phr of ahindered phenol stabilizer using the method described in Examples 75-82.Molded plaques showed YI of 7.7.

EXAMPLE 86

In this Example the resorcinol arylate polymer comprised structuralunits derived from resorcinol and a 1:1 mixture of iso- andterephthaloyl dichlorides. The Example used a resorcinol arylate blockcopolymer with bisphenol A polycarbonate containing about 25 wt. %carbonate units. As stabilizer additive, phosphorous acid was employedas 10 wt. % solution in deionized water which was mixed with the blockcopolymer before extrusion using a twin-screw extruder. The extrudedmixture was molded into plaques 2.5 inches square and one-eighth inchthick. The color of the disks was determined on a GretagMacbeth™Color-Eye 7000A colorimeter and reported as yellowness index (YI;according to ASTM D1925). A plaque containing 0.2 wt. % phosphorous acidhad an initial YI of 11.1. For comparison a similar plaque made withoutphosphorous acid had an initial YI of 20.1.

While the invention has been illustrated and described in typicalembodiments, it is not intended to be limited to the details shown,since various modifications and substitutions can be made withoutdeparting in any way from the spirit of the present invention. As such,further modifications and equivalents of the invention herein disclosedmay occur to persons skilled in the art using no more than routineexperimentation, and all such modifications and equivalents are believedto be within the spirit and scope of the invention as defined by thefollowing claims. All U.S. Patents cited herein are incorporated hereinby reference.

What is claimed is:
 1. A multilayer article comprising: a substratelayer comprising at least one thermoplastic polymer, thermoset polymer,cellulosic material, glass, or metal, and at least one coating layerthereon, said coating layer comprising at least one auxiliary colorstabilizer additive and a thermally stable polymer comprising resorcinolarylate polyester chain members substantially free of anhydride linkageslinking at least two mers of the polymer chain, prepared by aninterfacial method comprising the steps of: (a) combining at least oneresorcinol moiety and at least one catalyst in a mixture of water and atleast one organic solvent substantially immiscible with water; and (b)adding to the mixture from (a) at least one dicarboxylic acid dichloridewhile maintaining the pH between 3 and 8.5 through the presence of anacid acceptor, wherein the total molar amount of acid chloride groups isstoichiometrically deficient relative to the total molar amount ofphenolic groups.
 2. The article according to claim 1 wherein thesubstrate comprises at least one homo- or copolymeric aliphatic olefinor functionalized olefin polymer, polycarbonate, polyester or additionpolymer of an alkenylaromatic compound.
 3. The article according toclaim 2 wherein the substrate comprises at least one polyolefinhomopolymer, polyethylene, polypropylene, thermoplastic polyolefin,bisphenol A homo- or copolycarbonate, poly(alkylene terephthalate), orABS or ASA copolymer.
 4. The article according to claim 1 wherein theauxiliary color stabilizer additive is at least one member selected fromthe group consisting of a UV absorber, a hindered phenol, a phosphite,and phosphorous acid, and mixtures thereof.
 5. The article according toclaim 1 wherein the coating layer further comprises at least onecolorant.
 6. The article according to claim 1 wherein the substratecontains at least one of fillers and colorants.
 7. The article accordingto claim 1 further comprising an intermediate layer disposed betweensaid coating and substrate layers.
 8. The article according to claim 7wherein the intermediate layer contains at least one of fillers andcolorants.
 9. The article according to claim 1 which is an aircraft,automotive, truck, military vehicle, military aircraft, militarywater-borne vehicle, scooter, or motorcycle exterior or interiorcomponent, panel, quarter panel, rocker panel, trim, fender, door,decklid, trunklid, hood, bonnet, roof, bumper, fascia, grill, mirrorhousing, pillar applique, cladding, body side molding, wheel cover,hubcap, door handle, spoiler, window frame, headlamp bezel, headlamp,tail lamp, tail lamp housing, tail lamp bezel, license plate enclosure,roof rack, or running board; an enclosure, housing, panel, part, or trimfor an outdoor vehicle or device, an electrical or telecommunicationdevice, network interface device, outdoor furniture, aircraft, boat ormarine equipment, outboard motor, depth finder, personal water-craft,jet-ski, pool, spa, hot-tub, step, step covering, automatic tellermachine (ATM), lawn or garden tractor, lawn mower, tool, sportingequipment, toy, snowmobile, recreational vehicle, golf course marker, orplayground equipment; an enclosure, housing, panel, part, or trim for acomputer, desk-top computer, portable computer, lap-top computer,palm-held computer, monitor, printer, keyboard, FAX machine, copier,telephone, mobile phone, phone bezel, radio sender, radio receiver,meter, antenna, light fixture, lighting appliance, transformer, or airconditioner; an article used in building or construction, glazing,roofing, window, window trim, floor, wall panel, door, door trim,countertop, decorative window furnishing or treatment; a treated glasscover for a picture, painting, poster, or display item; a protectedgraphic; an outdoor or indoor sign; optical lens; ophthalmic lens;corrective ophthalmic lens; implantable ophthalmic lens; an article madefrom a plastic-wood combination; a utility pit cover; shoe lace;cladding or seating for public transportation; cladding or seating fortrains, subways, or buses; cladding for satellite dishes; coated helmetor personal protective equipment; coated synthetic or natural textiles;coated photographic film or photographic print; coated painted article;coated dyed article; coated fluorescent article; or coated foam article.10. A method for preparing a multilayer article which comprises applyingat least one thermally stable coating layer to a second layer, saidsecond layer comprising at least one thermoplastic polymer, thermosetpolymer, cellulosic material, glass, or metal, and said coating layercomprising at least one auxiliary color stabilizer additive and athermally stable polymer comprising resorcinol arylate polyester chainmembers substantially free of anhydride linkages linking at least twomers of the polymer chain, prepared by an interfacial method comprisingthe steps of: (a) combining at least one resorcinol moiety and at leastone catalyst in a mixture of water and at least one organic solventsubstantially immiscible with water; and (b) adding to the mixture from(a) at least one dicarboxylic acid dichloride while maintaining the pHbetween 3 and 8.5 through the presence of an acid acceptor, wherein thetotal molar amount of acid chloride groups is stoichiometricallydeficient relative to the total molar amount of phenolic groups.
 11. Themethod according to claim 10 wherein the substrate comprises at leastone homo- or copolymeric aliphatic olefin or functionalized olefinpolymer, polycarbonate, polyester or addition polymer of analkenylaromatic compound.
 12. The method according to claim 11 whereinthe substrate comprises at least one polyolefin homopolymer,polyethylene, polypropylene, thermoplastic polyolefin, bisphenol A homo-or copolycarbonate, poly(alkylene terephthalate), or ABS or ASAcopolymer.
 13. The method according to claim 10 wherein the auxiliarycolor stabilizer additive is at least one member selected from the groupconsisting of a UV absorber, a hindered phenol, a phosphite, andphosphorous acid, and mixtures thereof.
 14. The method according toclaim 10 wherein the coating layer further comprises at least onecolorant.
 15. The method according to claim 10 wherein the substratecontains at least one of fillers and colorants.
 16. The method accordingto claim 10 further comprising an intermediate layer disposed betweensaid coating and substrate layers.
 17. The method according to claim 16wherein the intermediate layer contains at least one of fillers andcolorants.
 18. The method according to claim 10 wherein said multilayerarticle is further applied to a substrate layer.
 19. The methodaccording to claim 18 wherein the substrate layer comprises at least onehomo- or copolymeric aliphatic olefin or functionalized olefin polymer,polycarbonate, polyester or addition polymer of an alkenylaromaticcompound.
 20. A multilayer article comprising: a substrate layercomprising at least one thermoplastic polymer, thermoset polymer,cellulosic material, glass, or metal, and at least one coating layerthereon, said coating layer comprising at least one auxiliary colorstabilizer additive and a thermally stable polymer consistingessentially of resorcinol arylate polyester chain members substantiallyfree of anhydride linkages linking at least two mers of the polymerchain, prepared by an interfacial method, comprising the steps of: (a)combining at least one resorcinol moiety and at least one catalyst in amixture of water and at least one organic solvent substantiallyimmiscible with water; and (b) adding to the mixture from (a) at leastone dicarboxylic acid dichloride while maintaining the pH between 3 and8.5 through the presence of an acid acceptor, wherein the total molaramount of acid chloride groups is stoichiometrically deficient relativeto the total molar amount of phenolic groups.
 21. The article accordingto claim 20 wherein the substrate comprises at least one homo- orcopolymeric aliphatic olefin or functionalized olefin polymer,polycarbonate, polyester or addition polymer of an alkenylaromaticcompound.
 22. The article according to claim 21 wherein the substratecomprises at least one polyolefin homopolymer, polyethylene,polypropylene, thermoplastic polyolefin, bisphenol A homo- orcopolycarbonate, poly(alkylene terephthalate), or ABS or ASA copolymer.23. The article according to claim 20 wherein the auxiliary colorstabilizer additive is at least one member selected from the groupconsisting of a UV absorber, a hindered phenol, a phosphite, andphosphorous acid, and mixtures thereof.
 24. The article according toclaim 20 wherein the coating layer further comprises at least onecolorant.
 25. The article according to claim 20 wherein the substratecontains at least one of fillers and colorants.
 26. The articleaccording to claim 20 further comprising an intermediate layer disposedbetween said coating and substrate layers.
 27. The article according toclaim 26 wherein the intermediate layer contains at least one of fillersand colorants.
 28. The article according to claim 20 which is anaircraft, automotive, truck, military vehicle, military aircraft,military water-borne vehicle, scooter, or motorcycle exterior orinterior component, panel, quarter panel, rocker panel, trim, fender,door, decklid, trunklid, hood, bonnet, roof, bumper, fascia, grill,mirror housing, pillar applique, cladding, body side molding, wheelcover, hubcap, door handle, spoiler, window frame, headlamp bezel,headlamp, tail lamp, tail lamp housing, tail lamp bezel, license plateenclosure, roof rack, or running board; an enclosure, housing, panel,part, or trim for an outdoor vehicle or device, an electrical ortelecommunication device, network interface device, outdoor furniture,aircraft, boat or marine equipment, outboard motor, depth finder,personal water-craft, jet-ski, pool, spa, hot-tub, step, step covering,automatic teller machine (ATM), lawn or garden tractor, lawn mower,tool, sporting equipment, toy, snowmobile, recreational vehicle, golfcourse marker, or playground equipment; an enclosure, housing, panel,part, or trim for a computer, desk-top computer, portable computer,lap-top computer, palm-held computer, monitor, printer, keyboard, FAXmachine, copier, telephone, mobile phone, phone bezel, radio sender,radio receiver, meter, antenna, light fixture, lighting appliance,transformer, or air conditioner; an article used in building orconstruction, glazing, roofing, window, window trim, floor, wall panel,door, door trim, countertop, decorative window furnishing or treatment;a treated glass cover for a picture, painting, poster, or display item;a protected graphic; an outdoor or indoor sign; optical lens; ophthalmiclens; corrective ophthalmic lens; implantable ophthalmic lens; anarticle made from a plastic-wood combination; a utility pit cover; shoelace; cladding or seating for public transportation; cladding or seatingfor trains, subways, or buses; cladding for satellite dishes; coatedhelmet or personal protective equipment; coated synthetic or naturaltextiles; coated photographic film or photographic print; coated paintedarticle; coated dyed article; coated fluorescent article; or coated foamarticle.
 29. A method for preparing a multilayer article which comprisesapplying at least one thermally stable coating layer to a second layer,said second layer comprising at least one thermoplastic polymer,thermoset polymer, cellulosic material, glass, or metal, and saidcoating layer comprising at least one auxiliary color stabilizeradditive and a thermally stable polymer consisting essentially ofresorcinol arylate polyester chain members substantially free ofanhydride linkages linking at least two mers of the polymer chain,prepared by an interfacial method, comprising the steps of: (a)combining at least one resorcinol moiety and at least one catalyst in amixture of water and at least one organic solvent substantiallyimmiscible with water; and (b) adding to the mixture from (a) at leastone dicarboxylic acid dichloride while maintaining the pH between 3 and8.5 through the presence of an acid acceptor, wherein the total molaramount of acid chloride groups is stoichiometrically deficient relativeto the total molar amount of phenolic groups.
 30. The method accordingto claim 29 wherein the substrate comprises at least one homo- orcopolymeric aliphatic olefin or functionalized olefin polymer,polycarbonate, polyester or addition polymer of an alkenylaromaticcompound.
 31. The method according to claim 30 wherein the substratecomprises at least one polyolefin homopolymer, polyethylene,polypropylene, thermoplastic polyolefin, bisphenol A homo- orcopolycarbonate, poly(alkylene terephthalate), or ABS or ASA copolymer.32. The article according to claim 29 wherein the auxiliary colorstabilizer additive is at least one member selected from the groupconsisting of a UV absorber, a hindered phenol, a phosphite, andphosphorous acid, and mixtures thereof.
 33. The method according toclaim 29 wherein the coating layer further comprises at least onecolorant.
 34. The method according to claim 26 wherein the substratecontains at least one of fillers and colorants.
 35. The method accordingto claim 29 further comprising an intermediate layer disposed betweensaid coating and substrate layers.
 36. The method according to claim 35wherein the intermediate layer contains at least one of fillers andcolorants.
 37. The method according to claim 29 wherein said multilayerarticle is further applied to a substrate layer.
 38. The methodaccording to claim 37 wherein the substrate layer comprises at least onehomo- or copolymeric aliphatic olefin or functionalized olefin polymer,polycarbonate, polyester or addition polymer of an alkenylaromaticcompound.
 39. A multilayer article comprising: a substrate layercomprising at least one thermoplastic polymer, thermoset polymer,cellulosic material, glass, or metal, and at least one coating layerthereon, said coating layer comprising at least one auxiliary colorstabilizer additive and a thermally stable copolymer consistingessentially of resorcinol arylate polyester chain members in combinationwith C₃₋₂₀ straight chain alkylene, C₃₋₁₀ branched alkylene, or C₄₋₁₀cyclo- or bicyclo-alkylene chain members, substantially free ofanhydride linkages linking at least two mers of the polymer chain,prepared by an interfacial method, comprising the steps of (a) combiningat least one resorcinol moiety and at least one catalyst in a mixture ofwater and at least one organic solvent substantially immiscible withwater; and (b) adding to the mixture from (a) at least one dicarboxylicacid dichloride while maintaining the pH between 3 and 8.5 through thepresence of an acid acceptor, wherein the total molar amount of acidchloride groups is stoichiometrically deficient relative to the totalmolar amount of phenolic groups.
 40. The article according to claim 39wherein the substrate comprises at least one homo- or copolymericaliphatic olefin or functionalized olefin polymer, polycarbonate,polyester or addition polymer of an alkenylaromatic compound.
 41. Thearticle according to claim 40 wherein the substrate comprises at leastone polyolefin homopolymer, polyethylene, polypropylene, thermoplasticpolyolefin, bisphenol A homo- or copolycarbonate, poly(alkyleneterephthalate), or ABS or ASA copolymer.
 42. The article according toclaim 39 wherein the auxiliary color stabilizer additive is at least onemember selected from the group consisting of a UV absorber, a hinderedphenol, a phosphite, and phosphorous acid, and mixtures thereof.
 43. Thearticle according to claim 39 wherein the coating layer furthercomprises at least one colorant.
 44. The article according to claim 39wherein the substrate contains at least one of fillers and colorants.45. The article according to claim 39 further comprising an intermediatelayer disposed between said coating and substrate layers.
 46. Thearticle according to claim 45 wherein the intermediate layer contains atleast one of fillers and colorants.
 47. The article according to claim39 which is an aircraft, automotive, truck, military vehicle, militaryaircraft, military water-borne vehicle, scooter, or motorcycle exterioror interior component, panel, quarter panel, rocker panel, trim, fender,door, decklid, trunklid, hood, bonnet, roof, bumper, fascia, grill,mirror housing, pillar applique, cladding, body side molding, wheelcover, hubcap, door handle, spoiler, window frame, headlamp bezel,headlamp, tail lamp, tail lamp housing, tail lamp bezel, license plateenclosure, roof rack, or running board; an enclosure, housing, panel,part, or trim for an outdoor vehicle or device, an electrical ortelecommunication device, network interface device, outdoor furniture,aircraft, boat or marine equipment, outboard motor, depth finder,personal water-craft, jet-ski, pool, spa, hot-tub, step, step covering,automatic teller machine (ATM), lawn or garden tractor, lawn mower,tool, sporting equipment, toy, snowmobile, recreational vehicle, golfcourse marker, or playground equipment; an enclosure, housing, panel,part, or trim for a computer, desk-top computer, portable computer,lap-top computer, palm-held computer, monitor, printer, keyboard, FAXmachine, copier, telephone, mobile phone, phone bezel, radio sender,radio receiver, meter, antenna, light fixture, lighting appliance,transformer, or air conditioner; an article used in building orconstruction, glazing, roofing, window, window trim, floor, wall panel,door, door trim, countertop, decorative window furnishing or treatment,a treated glass cover for a picture, painting, poster, or display item;a protected graphic; an outdoor or indoor sign; optical lens; ophthalmiclens; corrective ophthalmic lens; implantable ophthalmic lens; anarticle made from a plastic-wood combination; a utility pit cover; shoelace; cladding or seating for public transportation; cladding or seatingfor trains, subways, or buses; cladding for satellite dishes; coatedhelmet or personal protective equipment; coated synthetic or naturaltextiles; coated photographic film or photographic print; coated paintedarticle; coated dyed article; coated fluorescent article; or coated foamarticle.
 48. A method for preparing a multilayer article which comprisesapplying at least one thermally stable coating layer to a second layer,said second layer comprising at least one thermoplastic polymer,thermoset polymer, cellulosic material, glass, or metal, and saidcoating layer comprising at least one auxiliary color stabilizeradditive and a thermally stable copolymer consisting essentially ofresorcinol arylate polyester chain members in combination with C₃₋₂₀straight chain alkylene, C₃₋₁₀ branched alkylene, or C₄₋₁₀ cyclo- orbicyclo-alkylene chain members, substantially free of anhydride linkageslinking at least two mers of the polymer chain, prepared by aninterfacial method, comprising the steps of: (a) combining at least oneresorcinol moiety and at least one catalyst in a mixture of water and atleast one organic solvent substantially immiscible with water; and (b)adding to the mixture from (a) at least one dicarboxylic acid dichloridewhile maintaining the pH between 3 and 8.5 through the presence of anacid acceptor, wherein the total molar amount of acid chloride groups isstoichiometrically deficient relative to the total molar amount ofphenolic groups.
 49. The method according to claim 48 wherein thesubstrate comprises at least one homo- or copolymeric aliphatic olefinor functionalized olefin polymer, polycarbonate, polyester or additionpolymer of an alkenylaromatic compound.
 50. The method according toclaim 49 wherein the substrate comprises at least one polyolefinhomopolymer, polyethylene, polypropylene, thermoplastic polyolefin,bisphenol A homo- or copolycarbonate, poly(alkylene terephthalate), orABS or ASA copolymer.
 51. The article according to claim 48 wherein theauxiliary color stabilizer additive is at least one member selected fromthe group consisting of a UV absorber, a hindered phenol, a phosphate,and phosphorous acid, and mixtures thereof.
 52. The method according toclaim 48 wherein the coating layer further comprises at least onecolorant.
 53. The method according to claim 48 wherein the substratecontains at least one of fillers and colorants.
 54. The method accordingto claim 48 further comprising an intermediate layer disposed betweensaid coating and substrate layers.
 55. The method according to claim 54wherein the intermediate layer contains at least one of fillers andcolorants.
 56. The method according to claim 48 wherein said multilayerarticle is further applied to a substrate layer.
 57. The methodaccording to claim 56 wherein the substrate layer comprises at least onehomo- or copolymeric aliphatic olefin or functionalized olefin polymer,polycarbonate, polyester or addition polymer of an alkenylaromaticcompound.
 58. A multilayer article comprising: a substrate layercomprising at least one thermoplastic polymer, thermoset polymer,cellulosic material, glass, or metal, and at least one coating layerthereon, said coating layer comprising at least one auxiliary colorstabilizer additive and a thermally stable block copolymer consistingessentially of resorcinol arylate polyester segments in combination withorganic carbonate segments, substantially free of anhydride linkageslinking at least two mers of the polymer chain, prepared by aninterfacial method, comprising the steps of: (a) combining at least oneresorcinol moiety and at least one catalyst in a mixture of water and atleast one organic solvent substantially immiscible with water; and (b)adding to the mixture from (a) at least one dicarboxylic acid dichloridewhile maintaining the pH between 3 and 8.5 through the presence of anacid acceptor, wherein the total molar amount of acid chloride groups isstoichiometrically deficient relative to the total molar amount ofphenolic groups.
 59. The article according to claim 58 wherein thesubstrate comprises at least one homo- or copolymeric aliphatic olefinor functionalized olefin polymer, polycarbonate, polyester or additionpolymer of an alkenylaromatic compound.
 60. The article according toclaim 59 wherein the substrate comprises at least one polyolefinhomopolymer, polyethylene, polypropylene, thermoplastic polyolefin,bisphenol A homo- or copolycarbonate, poly(alkylene terephthalate), orABS or ASA copolymer.
 61. The article according to claim 58 wherein theauxiliary color stabilizer additive is at least one member selected fromthe group consisting of a UV absorber, a hindered phenol, a phosphite,and phosphorous acid, and mixtures thereof.
 62. The article according toclaim 58 wherein the coating layer further comprises at least onecolorant.
 63. The article according to claim 58 wherein the substratecontains at least one of fillers and colorants.
 64. The articleaccording to claim 58 further comprising an intermediate layer disposedbetween said coating and substrate layers.
 65. The article according toclaim 64 wherein the intermediate layer contains at least one of fillersand colorants.
 66. The article according to claim 58 which is anaircraft, automotive, truck, military vehicle, military aircraft,military water-borne vehicle, scooter, or motorcycle exterior orinterior component, panel, quarter panel, rocker panel, trim, fender,door, decklid, trunklid, hood, bonnet, roof, bumper, fascia, grill,mirror housing, pillar applique, cladding, body side molding, wheelcover, hubcap, door handle, spoiler, window frame, headlamp bezel,headlamp, tail lamp, tail lamp housing, tail lamp bezel, license plateenclosure, roof rack, or running board; an enclosure, housing, panel,part, or trim for an outdoor vehicle or device, an electrical ortelecommunication device, network interface device, outdoor furniture,aircraft, boat or marine equipment, outboard motor, depth finder,personal water-craft, jet-ski, pool, spa, hot-tub, step, step covering,automatic teller machine (ATM), lawn or garden tractor, lawn mower,tool, sporting equipment, toy, snowmobile, recreational vehicle, golfcourse marker, or playground equipment; an enclosure, housing, panel,part, or trim for a computer, desk-top computer, portable computer,lap-top computer, palm-held computer, monitor, printer, keyboard, FAXmachine, copier, telephone, mobile phone, phone bezel, radio sender,radio receiver, meter, antenna, light fixture, lighting appliance,transformer, or air conditioner; an article used in building orconstruction, glazing, roofing, window, window trim, floor, wall panel,door, door trim, countertop, decorative window furnishing or treatment;a treated glass cover for a picture, painting, poster, or display item;a protected graphic; an outdoor or indoor sign; optical lens; ophthalmiclens; corrective ophthalmic lens; implantable ophthalmic lens; anarticle made from a plastic-wood combination; a utility pit cover; shoelace; cladding or seating for public transportation; cladding or seatingfor trains, subways, or buses; cladding for satellite dishes; coatedhelmet or personal protective equipment; coated synthetic or naturaltextiles; coated photographic film or photographic print; coated paintedarticle; coated dyed article; coated fluorescent article; or coated foamarticle.
 67. A method for preparing a multilayer article which comprisesapplying at least one thermally stable coating layer to a second layer,said second layer comprising at least one thermoplastic polymer,thermoset polymer, cellulosic material, glass, or metal, and saidcoating layer comprising at least one auxiliary color stabilizeradditive and a thermally stable block copolymer consisting essentiallyof resorcinol arylate polyester segments in combination with organiccarbonate segments, substantially free of anhydride linkages linking atleast two mers of the polymer chain, prepared by an interfacial method,comprising the steps of: (a) combining at least one resorcinol moietyand at least one catalyst in a mixture of water and at least one organicsolvent substantially immiscible with water; and (b) adding to themixture from (a) at least one dicarboxylic acid dichloride whilemaintaining the pH between 3 and 8.5 through the presence of an acidacceptor, wherein the total molar amount of acid chloride groups isstoichiometrically deficient relative to the total molar amount ofphenolic groups.
 68. The method according to claim 67 wherein thesubstrate comprises at least one homo- or copolymeric aliphatic olefinor functionalized olefin polymer, polycarbonate, polyester or additionpolymer of an alkenylaromatic compound.
 69. The method according toclaim 68 wherein the substrate comprises at least one polyolefinhomopolymer, polyethylene, polypropylene, thermoplastic polyolefin,bisphenol A homo- or copolycarbonate, poly(alkylene terephthalate), orABS or ASA copolymer.
 70. The method according to claim 67 wherein thecoating layer further comprises at least one colorant.
 71. The methodaccording to claim 67 wherein the substrate contains at least one offillers and colorants.
 72. The method according to claim 67 furthercomprising an intermediate layer disposed between said coating andsubstrate layers.
 73. The method according to claim 72 wherein theintermediate layer contains at least one of fillers and colorants. 74.The method according to claim 67 wherein said multilayer article isfurther applied to a substrate layer.
 75. The method according to claim74 wherein the substrate layer comprises at least one homo- orcopolymeric aliphatic olefin or functionalized olefin polymer,polycarbonate, polyester or addition polymer of an alkenylaromaticcompound.